THIN-SHEET FORMED PRODUCT HAVING THREE-DIMENSIONAL SURFACE MICROSTRUCTURE, FUEL CELL SEPARATOR, AND METHOD AND FACILITY FOR MANUFACTURING SAME

Abstract

To provide a sheet formed product that, in addition to being thin, has a small groove interval, groove width, and groove depth, that has a large contact surface area with oxygen gas or hydrogen gas, that is suitable for simply and at low cost producing a lightweight compact separator, and a manufacturing method for same. In the sheet formed product (amorphous thin sheet) according to the present invention, a metal matrix on which is formed a passivation layer on a surface layer thereof and that exhibits corrosion resistance has a three-dimensional surface structure, for example a groove-like uneven shape on a surface thereof. On the front surface having the uneven shape (or also on the back surface), particles of a conductive material component penetrate the passivation layer, and are exposed on the surface without being in solid solution in the metal matrix.

Claims

1. A thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness, and comprising a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof, wherein a conductive material that penetrates the passivation layer of the surface layer region of the passivation layer and is electrically continuous with the metal matrix in the interior is partially exposed on a protruding front end surface in the three-dimensional surface structure of the thin-sheet formed product and on a back surface opposite to the front end surface.

2. The thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, wherein the front end surface is provided with the conductive material at a higher density than the back surface.

3. The thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, wherein the conductive material is a granular, flaky, or amorphous precipitate, and, over the whole surface layer region of the surface layer of the passivation layer, is exposed on the surface, penetrates the passivation layer, and is electrically continuous with the metal matrix in the interior.

4. The thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, wherein the metal matrix is amorphous, and the conductive material is WC or graphite.

5. The thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, wherein the metal matrix is an amorphous alloy containing Si and Mn.

6. The thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, wherein the metal matrix is an amorphous alloy having the composition Fe55Cr10Mo2Ni7Mn1.5P19B3Si2.5, Fe56.6Cr9Ni8Mo2Cu0.2Si2.5Mn1.5Nb0.7P19C0.5, Fe56Cr10Mo2Ni8P19C1Si2.5Mn1.5, or Ni65Cr15P16B4 (all numerical values are at %).

7. The thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, obtained by melting and mixing raw material metal powder including metal material powder from which the metal matrix is constituted and powder of the conductive material, while spraying the raw material metal powder together with flame and an assist gas using a required thermal spray gun; directing the spray together with the flame at the required distance and angle towards an inverted three-dimensional surface structure of a forming die that has the inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness corresponding to the inverted shape of the three-dimensional surface microstructure with uneven portions of a desired depth and thickness, in which the conductive material is provided on the bottom surfaces of concave portions of the inverted three-dimensional surface structure, and that has been heated to a desired temperature in advance; commencing cooling of the raw material metal powder before the melted and mixed raw material metal powder reaches the forming die by the flow of a predetermined cooling medium that is sprayed around the raw material metal powder; cohesively laminating the raw material metal powder that has reached a required solidified state or semi-solidified state on the uneven portions of the inverted three-dimensional surface microstructure of the forming die so that the concave portions of the uneven portions is filled, and continuing to spray the raw material metal powder until a required deposition thickness is achieved; subsequently performing upsetting press forming on the surface of the cohesive laminate using a predetermined tool to apply a desired surface structure, and then cooling the cohesive laminate; and releasing the cohesive laminate from the forming die.

8. A separator for a polymer electrolyte fuel cell, comprising the thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 1, the thin-sheet formed product including groove-like uneven portions of a desired depth and thickness.

9. A method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness, the method comprising: melting and mixing raw material metal powder including metal material powder from which a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof is constituted and conductive material powder, while spraying the raw material metal powder together with flame and an assist gas using a required thermal spray gun; directing the spray together with the flame at the required distance and angle towards an inverted three-dimensional surface structure of a forming die that has the inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness corresponding to the inverted shape of the three-dimensional surface microstructure with uneven portions of a desired depth and thickness and that has been heated to a desired temperature in advance; commencing cooling of the raw material metal powder before the melted and mixed raw material metal powder reaches the forming die by the flow of a predetermined cooling medium that is sprayed around the raw material metal powder; cohesively laminating the raw material metal powder that has reached a required solidified state or semi-solidified state on the uneven portions of the inverted three-dimensional surface microstructure of the forming die so that the concave portions of the uneven portions is filled, and continuing to spray the raw material metal powder until a required deposition thickness is achieved; subsequently performing upsetting press forming on the surface of the cohesive laminate using a predetermined tool in a desired temperature range to apply a desired surface structure, and then cooling the cohesive laminate; and releasing the cohesive laminate from the forming die.

10. The method for manufacturing a thin-sheet formed product according to claim 9, comprising obtaining a high concentration of the conductive material on a front end surface of the three-dimensional surface microstructure with uneven portions of a desired depth and thickness by attaching and fixing the powder of the conductive material on the bottom surfaces of the concave portions of the inverted three-dimensional surface structure using a spraying method or coating method in advance, and then spraying and cohesively laminating the raw material metal powder in a solidified state or a semi-solidified state.

11. The method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 9, wherein the upsetting press forming on the surface of the cohesive laminate in the desired temperature range is by press forming.

12. The method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 9, wherein the upsetting press forming on the surface of the cohesive laminate in the desired temperature range is by roll forming.

13. A method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness, the method comprising: melting and mixing raw material metal powder including metal material powder from which a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof is constituted, while spraying the raw material metal powder together with flame and an assist gas using a required thermal spray gun; directing the spray together with the flame at the required distance and angle towards an inverted three-dimensional surface structure of a forming die that has the inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness corresponding to the inverted shape of the three-dimensional surface microstructure with uneven portions of a desired depth and thickness, in which the conductive material is arranged on the bottom surfaces of the concave portions of the inverted three-dimensional surface microstructure using a spraying method or coating method in advance, and that has been heated to a desired temperature in advance; commencing cooling of the raw material metal powder before the melted and mixed raw material metal powder reaches the forming die by the flow of a predetermined cooling medium that is sprayed around the raw material metal powder; cohesively laminating the raw material metal powder that has reached a required solidified state or semi-solidified state on the uneven portions of the inverted three-dimensional surface microstructure of the forming die so that the concave portions of the uneven portions is filled, and continuing to spray the raw material metal powder until a required deposition thickness is achieved; subsequently performing upsetting press forming on the surface of the cohesive laminate using a predetermined tool in a desired temperature range to apply a desired surface structure, and then cooling the cohesive laminate; and releasing the cohesive laminate from the forming die.

14. The method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 13, comprising attaching and fixing the powder of the conductive material on the surface of the cohesive laminate using a spraying method or coating method in advance, and then performing the upsetting press forming on the surface of the cohesive laminate in a desired temperature range by a press method.

15. The method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 13, comprising attaching and fixing the powder of the conductive material on the surface of the cohesive laminate using a spraying method or coating method in advance, and then performing the upsetting press forming on the surface of the cohesive laminate in a desired temperature range by roll forming.

16. The method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 9, comprising: attaching and fixing the powder of the conductive material to the bottom surfaces of the concave portions of the inverted three-dimensional surface microstructure of the forming die using a spraying method or coating method in advance, and then placing, on a transport unit of a transport device, the forming die so that the inverted three-dimensional surface structure faces upward; pre-heating the forming die to a desired temperature by transporting the transport unit on which the forming die is placed to a heating device position for preheating; transporting the transport unit on which the preheated forming die is placed to a thermal spray unit position including the thermal spray gun, and cohesively laminating, onto the inverted three-dimensional surface structure of the forming die, a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof by spraying using the thermal spray gun; transporting the transport unit on which the forming die including the cohesive laminate deposited thereon is placed, to an upsetting press forming unit, applying a desired surface structure to the cohesive laminate on the forming die by upsetting press forming by either press forming or roll forming, and then cooling the forming die; and releasing the cohesive laminate from the forming die.

17. The method for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 9, comprising: releasing the cohesive laminate from the forming die after the upsetting press forming, performing an additional forming process on the released cohesive laminate by warm pressing using an additional forming die to apply a desired surface structure, and then cooling the cohesive laminate, and releasing the cohesive laminate from the additional forming die.

18. A facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness, the facility comprising a transport device that transports a forming die having an inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness, the forming die being placed in a state where the inverted three-dimensional surface structure facing upward, wherein a heating device for preheating the forming die; an ultraquenching transition control injector that melts and mixes raw material metal powder, while spraying the raw material metal powder together with flame and an assist gas using a required thermal spray gun, that commences cooling of the raw material metal powder before the melted and mixed raw material metal powder reaches the forming die by the flow of a predetermined cooling medium sprayed around the raw material metal powder, while spraying the raw material metal powder together with the flame, and that cohesively laminates, onto the inverted three-dimensional surface microstructure of the forming die, a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof, by spraying of the raw material metal powder that has reached a required solidified state or semi-solidified state; an upsetting device that performs upsetting press forming on the cohesive laminate in a desired temperature range using a predetermined tool; a device that cools the forming die having the cohesive laminate on which a desired surface structure is applied; and a releasing device that releases the thin-sheet formed product that is the cohesive laminate from the forming die, are arranged in that order on a transport path of the transport device.

19. The facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 18, wherein a conductive material arranging device that applies a conductive material component on a surface of the inverted three-dimensional surface structure of the forming die, by coating or spraying, is disposed in a position on the transport path of the transport device on the upstream side of the heating device.

20. The facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 18, further comprising, in addition to the transport device, a sizing press forming facility using a warm press device or a warm roll forming facility using a mill roll that use an additional forming die having a desired additional forming shape formed on a surface thereof for the thin-sheet formed product that has been released from the forming die.

21. A facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness, the facility comprising a transport device that transports a forming die having an inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness, the forming die being placed in a state where the inverted three-dimensional surface structure facing upward, wherein a lubricant and releasing agent application unit that performs a step of applying lubricant and releasing agent to the inverted three-dimensional surface structure of the forming die; a conductive material arranging unit that performs a step of applying by coating or spraying conductive material powder on the inverted three-dimensional surface structure of the forming die to which the lubricant and releasing agent has been applied; a preheating and temperature equalizing unit that performs a step of preheating and equalizing the temperature of the forming die; an ultraquenching transition control injection forming unit that performs a step of melting and mixing raw material metal powder, while spraying the raw material metal powder together with flame and an assist gas using a required thermal spray gun, commencing cooling of the raw material metal powder before the melted and mixed raw material metal powder reaches the forming die by the flow of a predetermined cooling medium sprayed around the raw material metal powder, while spraying the raw material metal powder together with the flame, and cohesively laminating, onto the inverted three-dimensional surface microstructure of the forming die, a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof, by spraying of the raw material metal powder that has reached a required solidified state or semi-solidified state; a first processing unit that performs a step of performing upsetting press forming on the cohesive laminate in a desired temperature range using a predetermined tool; a heat radiation and cooling unit that performs a step of radiating heat from and cooling the forming die having the cohesive laminate on which a desired surface structure has been applied by the first processing unit; a releasing and product discharging unit that performs a step of releasing and discharging the thin-sheet formed product that is the cohesive laminate from the forming die; and a forming die cleaning unit that performs a step of cleaning the forming die from which the thin-sheet formed product has been released, are arranged in this order on a transport path of the transport device.

22. The facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 19, wherein a preheating and temperature equalizing unit that performs a step of preheating and equalizing the temperature of the forming die including the inverted three-dimensional surface structure, on which the metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof is cohesively laminated, is disposed upstream of the first processing unit.

23. A facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness, comprising a transport device that transports a work piece of each desired operation, wherein a spray forming die installation unit that performs a step of feeding and setting a spray forming die having an inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness in a state where the inverted three-dimensional surface structure facing upward; a lubricant and releasing agent application unit; a conductive material arranging unit; a preheating and temperature equalizing unit; an ultraquenching transition control injection forming unit; a heat radiation and cooling unit; a releasing and formed product discharging unit that performs a step of releasing a spray formed product from the spray forming die, temporarily removing the spray formed product, and discharging the spray forming die; a first processing die installation unit that feeds a first processing die for upsetting press forming of the removed spray formed product; a lubricant and releasing agent application unit; a spray formed product setting unit that performs a step of feeding and setting in the first processing die the spray formed product that has been removed in the releasing and formed product discharging unit; a conductive material arranging unit; a preheating and temperature equalizing unit; a first processing unit that performs a step of upsetting press forming on the spray formed product; a heat radiation and cooling unit; a first processed product releasing and discharging unit that performs a step of releasing from the spray forming die and temporarily removing the first processed product on which upsetting press forming has been performed and discharging the first processing die; a second to Nth processing die installation unit that performs a step of feeding a second to Nth processing die for upsetting press forming in second and subsequent processing; an (N1)th processed product setting unit that performs a step of feeding and setting, to the second to the Nth processing die, the first processed product that has been removed in the releasing and formed product discharging unit, or an Nth processed product that has been released and removed from the Nth processing die in an Nth processed product releasing and discharging unit, described below; a lubricant and releasing agent application unit; a preheating and temperature equalizing unit; a second to Nth processing unit that performs a step of upsetting press forming on an (N1)th processed product; a heat radiation and cooling unit; and an Nth processed product releasing and discharging unit that performs a step of releasing, removing, and discharging the Nth processed product formed by the upsetting press forming from the second to Nth processing dies and discharging the Nth processing die, are arranged in this order on a transport path of the transport device.

24. The facility for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to claim 18, wherein the transport path of the transport device is arranged in an annular shape, a racetrack shape, or a linear shape.

25. A thin sheet with grooves, wherein a metal matrix exhibiting corrosion resistance by formation of a passivation layer on a surface layer thereof has groove-like unevenness on a surface thereof, and conductive material component particles are present on the surface having the unevenness so as to penetrate the passivation layer without being in solid solution.

26. A method of manufacturing a thin sheet with grooves, the method comprising: attaching a conductive material component to a surface of a die having groove-like unevenness; forming a corrosion-resistant alloy film with a thickness that fills the unevenness by spraying onto the surface; and performing warm pressing of the film immediately after forming the film to form, on a surface of a metal matrix exhibiting corrosion resistance by formation of a passivation layer, groove-like unevenness to which the conductive material component is fixed.

27. A facility for manufacturing a thin sheet with grooves, the facility comprising a transport device that transports a die that has groove-like unevenness on a surface thereof and in which a conductive material component is attached to the surface, in a state where the surface faces upward, wherein a heating device that preheats the die; a quenching thermal spray gun that forms, on the surface of the die, a corrosion-resistant alloy film, by spraying and melting metal powder together with flame and cooling the flame with a cooling gas; and a rolling mill that performs warm rolling of the corrosion-resistant alloy film immediately after the corrosion-resistant alloy film is formed, are arranged in that order on a transport path of the transport device.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0072] FIG. 1 is a side view illustrating the ultraquenching transition control injector in the attitude for use.

[0073] FIGS. 2A and 2B are views illustrating a large-sized ultraquenching transition control injector, FIG. 2A is a side view and FIG. 2B is a bottom view.

[0074] FIG. 3 is a perspective view generally illustrating a forming die to be used.

[0075] FIG. 4 is an overall plan view illustrating an uneven surface which is an inverted three-dimensional surface structure of the forming die of FIG. 3.

[0076] FIG. 5 is a side view illustrating an overall schematic view of a thin-sheet formed product production line.

[0077] FIG. 6 is a schematic perspective view illustrating important parts of a thin-sheet formed product production line.

[0078] FIG. 7 is an external view photograph illustrating a fine uneven surface of a thin-sheet formed product having a groove-like three-dimensional surface structure manufactured by the method of the present invention.

[0079] FIG. 8 is a microscope microstructure photograph illustrating a cross section of a thin-sheet formed product having a groove-like three-dimensional surface structure manufactured by the method of the present invention.

[0080] FIG. 9 is a view illustrating a DSC evaluation result of an amorphous alloy film containing Si and Mn.

[0081] FIG. 10 is a diagram illustrating a method for measuring the contact resistance of an amorphous alloy thin-sheet formed product having a groove-like three-dimensional surface structure.

[0082] FIG. 11 is a diagram showing the contact resistance measurement results of an amorphous alloy thin-sheet formed product having a groove-like three-dimensional surface structure.

[0083] FIG. 12 is a graph illustrating the results of evaluating the corrosion resistance of a thin-sheet formed product made of an amorphous alloy containing Si and Mn.

[0084] FIG. 13 is a conceptual diagram relating to performing an additional press forming process on a thin-sheet formed product having a groove-like three-dimensional surface structure created by the method of FIG. 6.

[0085] FIG. 14 is a top view illustrating an overall schematic view of a thin-sheet formed product manufacturing facility in which each manufacturing process is arranged in an annulus.

[0086] FIG. 15 is a top view illustrating an overall schematic view of another thin-sheet formed product manufacturing facility in which each manufacturing process is arranged in an annulus.

[0087] FIG. 16 is a top view showing an overall schematic view of a thin-sheet formed product manufacturing facility in which each manufacturing process is arranged in a racetrack shape.

DESCRIPTION OF EMBODIMENTS

[0088] An embodiment of the present invention is described below and illustrated in FIGS. 1 to 16. In this embodiment, on one surface of a thin-sheet formed product mainly made of an amorphous alloy a three-dimensional surface microstructure with an uneven portion having desired depth and thickness is formed, preferably as groove-shaped unevenness. Conductive material exists on both the front and back surfaces, penetrating a passivation layer of the surface layer, is exposed on the surface layer and the like, and is fixedly connected to and electrically continuous with an internal metal matrix. Note that the conductive material does not necessarily need to be dispersed in the metal matrix, and may be present only on the surface layer of the uneven surface or on the opposite surface to that surface.

[0089] A separator made of amorphous material, stainless steel, or titanium retains corrosion resistance by a passivation layer formed on the surface, but the passivation layer deteriorates the conductivity, so a material with good conductivity is required in the vicinity of the separator surface. Therefore, as an embodiment of the present invention, tungsten carbide (WC) having good conductivity is applied and arranged in advance preferably on the bottom surface of the uneven portion of the three-dimensional surface microstructure of the forming die. An amorphous alloy cohesive laminate is formed by spraying on the surface having an inverted three-dimensional surface structure corresponding to the fine inverted shape (transferred shape) having the uneven part with the desired depth and thickness of the forming die. This is immediately rolled so that the cohesive laminate plastically flows to improve the forming accuracy of the three-dimensional surface microstructure, eliminate internal pores, and even though it is made of amorphous material, conductive material such as WC is fixed and exposed, and a thin-sheet formed product is formed with good conductivity. The conductive material may be WC, carbon, graphite, or the like with an average particle diameter of about 1 to 10 m, and may be in various forms such as granular, flaky, flake, amorphous precipitate, or a mixture of powders such as these.

[0090] A quenching type spray gun (thermal spray gun) is used to form the thin-sheet formed product to be manufactured by spraying an amorphous alloy, and an ultraquenching transition control injector as illustrated in FIGS. 2A and 2B was used as the spray gun. Although the gun illustrated in FIG. 1 can be used, the gun illustrated in FIGS. 2A and 2B was used from the viewpoint of efficiency as described above. Mixed gas of oxygen and propane is used as fuel, and combustion flame is ejected from flame vents 5 outside of powder ejection ports 6, which are arranged at equal intervals in the widthwise direction. The powder material ejected from the powder ejection ports 6 is completely melted once in the combustion flame. Immediately after being melted, the material is deposited on the surface of a forming die having an inverted three-dimensional surface microstructure while being quenched with a refrigerant mist ejected from a mist ejection port 3 arranged outside the powder ejection ports 6, thereby forming an cohesive laminate. Since this spray gun ejects the material uniformly in the width direction, it is possible to produce a preferable thin-sheet formed product in which the cohesive laminate is formed uniformly in the width direction.

[0091] As a metal material to be sprayed by the above spray gun (FIGS. 2A and 2B), a gas atomized powder having a composition of Fe55Cr10Mo2Ni7Mn1.5P19B3Si2.5 (numerical value is at %) containing Si (silicon) and Mn (manganese) as impurities was used. This powder is likely to become amorphous even if it contains many impurities, and contains many impurities such as Si and Mn mixed when a low-grade raw material is used in the powder manufacturing process. Nevertheless, an amorphous material can be obtained by melting and quenching, and the resulting amorphous alloy film has excellent corrosion resistance and formability. Powders of other compositions that tend to become amorphous materials can be used to form other amorphous materials (for example, nickel-based Ni65Cr15P16B4, iron-based Fe56.6Cr9Ni8Mo2Cu0.2Si2.5Mn1.5Nb0.7P19C0.5, Fe56Cr10Mo2Ni8P19C1Si2.5Mn1.5 (at %)), but an amorphous alloy film of the same composition formed from a powder of the above composition which can be obtained at low cost was used. Since the cost is low, it is advantageous for producing a large number of thin-sheet formed products such as grooved thin sheets having a large surface area to be used as a material for a PEFC separator.

[0092] Regarding the bonding of the conductive powder to the passivation layer of the surface layer of the amorphous alloy thin-sheet formed product to be formed, tungsten carbide having an average particle diameter of 9 m (hereinafter referred to as WC) and graphite, which can be obtained at a low cost, was used as the powder.

[0093] As means for forming a three-dimensional surface microstructure having groove-like unevenness on the surface of the amorphous alloy thin-sheet formed product to which the conductive powder is fixed, the forming die illustrated in FIGS. 3 and 4 having, on the surface thereof, an engraved inverted three-dimensional surface microstructure with uneven portions with the required width and depth corresponding as an inverted shape to the three-dimensional surface structure was used. This forming die is made of SS400 standard steel material complying with JIS G 3101:2010 Rolled steels for general structure, on which is formed the inverted three-dimensional surface structure with groove-like unevenness having a depth of about 0.4 mm, a groove width of 0.4 mm, and a wall thickness of 0.4 mm as shown in the figure. However, the depth, groove width, and wall thickness may be changed depending on the part, and the cross-sectional shape of the groove is not limited to a rectangular wave as shown in the figure, but may be unevenness such as a trapezoidal wave or a sine curve, either singly or in combination, and so on. In addition, since SS400 steel material is used as the material of the forming die, it is easy to process by indentation of uneven grooves of the inverted three-dimensional surface structure, which is advantageous for manufacturing many disposable forming dies at low cost. Furthermore, FIG. 4 illustrates an example in which a single inverted three-dimensional surface structure having a length of 200 mm and a width of 150 mm is engraved on a forming die. The production efficiency is particularly good if the cohesive laminate released from the forming die after injection and cohesive lamination on the forming die on which is engraved a plurality of the inverted three-dimensional surface structures is divided into a plurality of pieces so that a plurality of thin-sheet formed products can be obtained.

[0094] Graphite mixed with WC was applied to the uneven surface of the inverted three-dimensional surface structure of the forming die, as described above. WC or the like may be adhered to the concave bottom surface, the convex top surface, and the convex side surface of the uneven surface of the inverted three-dimensional surface structure of the forming die, but it should be adhered to at least the concave bottom surface.

[0095] The above-described ultraquenching transition control injector or the like was installed on a production line (a production facility for thin sheets with grooves) as shown in FIG. 5. A hoop 15 uncoiled from a pickling coil made of ordinary steel is set between a payoff reel 7 and a coil winder 13, and the hoop 15 is moved toward the coil winder 13. The moving hoop 15 is used as a device for transporting the forming die.

[0096] In this production line, first, the hoop 15 uncoiled from the payoff reel 7 is heated by a preheater 8 with a propane flame. Next, after the heated hoop 15 is corrected in shape by a leveler 9 for the hoop 15, the above-mentioned forming die (to which a lubricant and a releasing agent are applied, then graphite mixed with WC is applied to the uneven surface with the inverted three-dimensional surface structure) is placed on the hoop 15. Then the hoop 15 on which the forming die is placed is transferred to a heating and equalizing device 10 where the forming die is heated together with the hoop 15 (preheating). An attaching device (not shown) for applying (or spraying) WC or the like to the uneven surface of the inverted three-dimensional surface structure of the forming die and attaching it may be provided immediately upstream of the heating and equalizing device 10.

[0097] When the forming die is placed on the surface of the hoop 15 as illustrated in FIG. 5 and is heated to a target temperature (about 250 C.), a ultraquenching transition control iRjector 11 injects the amorphous material onto the uneven surface of the inverted three-dimensional surface structure of the forming die. The forming die is immediately conveyed to a rolling mill 12 and the cohesive laminate made of the amorphous alloy is immediately rolled. The thickness of the cohesive laminate made of the amorphous alloy formed by the spraying is set to a thickness that completely fills the concave portions of the inverted three-dimensional surface structure of the forming die and also at least covers the convex surface. The above-mentioned rolling is performed while the cohesive laminate made of the amorphous alloy formed by thermal spraying is in a supercooled liquid phase state (430 C. to 480 C.). FIG. 6 illustrates an image of heating of a forming die, injection to the forming die, and immediate rolling.

[0098] Further, FIG. 7 shows a perspective external view photograph of the three-dimensional surface structure side (the side having the groove-shaped unevenness) of the amorphous alloy thin-sheet formed product obtained by releasing from the forming die. Note that FIG. 8 illustrates a microscope microstructure photograph of the cross-section of the amorphous alloy thin-sheet formed product before it was released from the forming die and was adhering to and cohesively laminated on the forming die (the forming die used in the processes in FIGS. 5 and 6 is at the bottom). When a DSC measurement of this amorphous alloy thin-sheet formed product was performed, a clear exothermic peak was obtained as shown in FIG. 9, indicating that the product was amorphous. It was confirmed that the amorphous rate was 90% or more.

[0099] The consistent resistance (contact resistance) of the amorphous alloy thin-sheet formed product produced as described above was measured by the measurement method illustrated in FIG. 10. The results are presented in FIG. 11.

[0100] The above-mentioned amorphous material of Fe55Cr10Mo2Ni7Mn1.5P19B3Si2.5 (at %) has a passivation layer formed on the surface layer (surface). The reason the contact resistance is reduced as the rolling pressure is increased as shown in FIG. 11 is considered to be because the WC, which is a conductor, penetrates the passivation layer and cuts into the metal matrix (It is electrically continuous with the metal matrix inside, is exposed on the outer surface, and extends between the inside and outside). Based on these results, it can be seen that the contact resistance that is increased by the formation of the passivation layer can be reduced by applying in advance the WC to the inverted three-dimensional surface structure of the forming die, spraying into the forming die to form the cohesive laminate, then immediately rolling, so that the WC is fixed to the surface of the three-dimensional surface structure side (groove-like unevenness side) of the amorphous alloy thin-sheet formed product that was cohesively laminated.

[0101] The results of the corrosion resistance evaluation (anode test) of the amorphous material (Fe55Cr10Mo2Ni7Mn1.5P19B3Si2.5 (at %)) are as shown in FIG. 12. The anode test measures the amount of current (=corrosion amount) flowing by changing the potential from negative to positive. The potential of 1000 mV is the voltage at the time of the maximum load such as when starting a car. It can be seen that the above amorphous material has a current density less than half that of SUS316L stainless steel, and the amount of corrosion is also reduced by halt

[0102] The thin-sheet formed product including the metal matrix having the passivation layer that provides corrosion resistance formed on the surface layer and having the three-dimensional surface microstructure with the required depth and thickness of uneven portions, which is obtained as described above (FIG. 6, etc.), may be again heated to 430 C. to 480 C. (the temperature range in which the amorphous material is in a supercooled liquid phase state), and additionally subjected to warm press forming/warm roll forming, to form a separator having a large contact area and high dimensional accuracy. FIG. 13 is a conceptual diagram relating to the execution of the warm press forming. For this additional warm press forming, the forming die used in FIG. 6 may be used as it is. However warm sizing press forming may be performed by repeatedly using an additional forming die formed of a steel material or a super-hard material generally called tool steel, high speed steel, die steel, or the like, which has better properties (for example, strength, toughness, hardness) at high temperatures than the forming die. Instead of the additional forming die set shown in FIG. 13, it is also possible to use an additional forming die set in which both the lower die and the upper die have a groove-like uneven shape of the inverted three-dimensional surface structure.

[0103] By additionally performing the warm press forming in this way, the cohesive laminate plastically flows to reduce the pores therein, while the WC in the surface layer with the groove-like uneven shape on the three-dimensional surface structure side of the amorphous alloy thin-sheet formed product more securely penetrates the passivation layer of the surface layer of the amorphous alloy and fixes. In addition the shape accuracy of the groove-like uneven shape on the three-dimensional surface structure side is improved.

[0104] The manufacture of a thin-sheet formed product having a three-dimensional surface microstructure with uneven portions of a desired depth and thickness according to the present invention is not limited to the method shown in FIG. 6 or the like.

[0105] For example, the following procedure may be adopted.

[0106] i) Lay the graphite powder on (the bottom of the groove-like uneven shape of the inverted three-dimensional surface structure on the upper surface of the forming die (lower die),

[0107] ii) Perform injection (injection by the above-mentioned spray gun) thereon to form the cohesive laminate made of an amorphous alloy having a thickness sufficiently covering the groove-like uneven shape portion having the inverted three-dimensional surface structure, and

[0108] iii) Press an additional forming die (upper die) having a flat pressing surface down onto the upper surface of the amorphous alloy cohesive laminate (then, the upper and lower dies are separated, and the cohesive laminate is separated and removed from the lower die).

[0109] In this case also, the thin-sheet formed product having the uneven shape suitable for a fuel cell (PEFC) separator can be produced, the same as described previously. Namely, the metal matrix with the passivation layer that provides corrosion resistance formed as a surface layer thereon has, in the surface thereof a groove-like uneven shape as the three-dimensional surface microstructure having uneven portions of the required depth and thickness, and the conductive material component on the surface having the uneven shape penetrates through the passivation layer becoming electrically continuous with the metal matrix, and being exposed on the surface.

[0110] Also, when using a quenching thermal spray gun as described above, in addition to the metal (powder material), conductive material component particles (having a high melting point so as not to melt in the flame and not form a solid solution in the molten metal) may be sprayed together with the flame. In this case, the conductive material component particles are not only distributed and present on the three-dimensional surface structure forming surface of the amorphous alloy thin-sheet formed product, but also in the interior of the thin-sheet formed product (metal matrix) and on the back surface opposite to the uneven surface, and a thin-sheet formed product having a preferable groove-like uneven shape can be produced.

[0111] The previously explained FIG. 10 illustrates a measurement for a formed product in which the conductive material component particles are distributed within the metal matrix and on the surface opposite to the uneven surface by spraying including the conductive material component particles (WC) as described above.

[0112] Further, the manufacturing facility according to the present invention for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure provided with uneven portions having the desired depth and thickness is not limited to the manufacturing facility shown in FIGS. 5, 6, and so on.

[0113] For example, as illustrated in FIGS. 14 and 15, the manufacturing facility may include,

1) a lubricant and releasing agent application unit that performs a step of applying lubricant and releasing agent to an inverted three-dimensional surface structure of a forming die that has the inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness corresponding to the inverted shape of the three-dimensional surface microstructure with uneven portions of a desired depth and thickness;
2) a conductive material arranging unit that performs a step of applying by coating or spraying conductive material powder on the inverted three-dimensional surface structure of the forming die to which the lubricant and releasing agent has been applied;
3) a preheating and temperature equalizing unit that performs a step of preheating and equalizing the temperature of the forming die;
4) an ultraquenching transition control injection forming unit that performs a step of melting and mixing raw material metal powder (preferably including conductive material powder), while spraying the raw material metal powder together with flame and an assist gas using a required thermal spray gun, commencing cooling of the raw material metal powder before the melted and mixed raw material metal powder reaches the forming die by the flow of a predetermined cooling medium sprayed around the raw material metal powder, while spraying the raw material metal powder together with the flame, and cohesively laminating, onto the inverted three-dimensional surface microstructure of the forming die, a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof, by spraying of the raw material metal powder that has reached a required solidified state or semi-solidified state;
5) a first processing unit that performs a step of performing upsetting press forming on the cohesive laminate in a desired temperature range using a predetermined tool;
6) a heat radiation and cooling unit that performs a step of radiating heat from and cooling the forming die having the cohesive laminate on which a desired surface structure has been applied by the first processing unit;
7) a releasing and product discharging unit that performs a step of releasing and discharging the thin-sheet formed product that is the cohesive laminate from the forming die; and
8) a forming die cleaning unit that performs a step of cleaning mainly the inverted three-dimensional surface microstructure portion of the forming die from which the thin-sheet formed product has been released, which are annularly arranged in this order on a transport path of a transport device.

[0114] In addition, if a preheating and temperature equalizing unit that performs a step of preheating and equalizing the temperature of the forming die including the inverted three-dimensional surface structure, on which the metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof is cohesively laminated, is disposed upstream of the first processing unit, plastic flow of the cohesive laminate is stably exhibited during the upsetting press forming in the first processing section, which is preferable.

[0115] Although a transport device having an annular transport path is shown, a transport device having a transport path of various shapes such as a linear shape or a racetrack shape may be used depending on the restrictions such as the installation space of the facility.

[0116] Further, the manufacturing facility according to the present invention for manufacturing a thin-sheet formed product having a three-dimensional surface microstructure provided with uneven portions having the desired depth and thickness is not limited to the manufacturing facility shown in FIGS. 5, 6, and so on.

[0117] For example, as shown in FIG. 16,

1) the manufacturing facility includes a transport device that transports a work piece of each desired operation, and in the facility,
2) a spray forming die installation unit that performs a step of feeding and setting a spray forming die having an inverted three-dimensional surface microstructure with uneven portions of a desired depth and thickness in a state where the inverted three-dimensional surface structure facing upward;
3) a lubricant and releasing agent application unit; a conductive material arranging unit; a preheating and temperature equalizing unit; an ultraquenching transition control injection forming unit; and a heat radiation and cooling unit;
4) a releasing and formed product discharging unit that performs a step of releasing a spray formed product from the spray forming die, temporarily removing the spray formed product, and discharging the spray forming die;
5) a first processing die installation unit that feeds a first processing die for upsetting press forming of the removed spray formed product;
6) a lubricant and releasing agent application unit;
7) a spray formed product setting unit that performs a step of feeding and setting in the first processing die the spray formed product that has been removed in the releasing and formed product discharging unit;
8) a conductive material arranging unit; and a preheating and temperature equalizing unit;
9) a first processing unit that performs a step of upsetting press forming on the spray formed product;
10) a heat radiation and cooling unit;
11) a first processed product releasing and discharging unit that performs a step of releasing from the spray forming die and temporarily removing the first processed product on which upsetting press forming has been performed and discharging the first processing die;
12) a second to Nth processing die installation unit that performs a step of feeding a second to Nth processing die for upsetting press forming in second and subsequent processing;
13) an (N1)th processed product setting unit that performs a step of feeding and setting, to the second to the Nth processing die, the first processed product that has been removed in the releasing and formed product discharging unit, or an Nth processed product that has been released and removed from the Nth processing die in an Nth processed product releasing and discharging unit, described below;
14) a lubricant and releasing agent application unit; and a preheating and temperature equalizing unit;
15) a second to Nth processing unit that performs a step of upsetting press forming on an (N1)th processed product;
16) a heat radiation and cooling unit; and
17) an Nth processed product releasing and discharging unit that performs a step of releasing, removing, and discharging the Nth processed product formed by the upsetting press forming from the second to Nth processing dies and discharging the Nth processing die, are arranged in this order on a transport path of the transport device.

[0118] As described above, by performing upsetting press forming, by using not only the first processing die but also the second to Nth processing dies which are preheated and equalized in temperature, on the spray formed product formed by cohesively laminating, on the inverted three-dimensional surface structure, a metal matrix exhibiting corrosion resistance by the formation of a passivation layer on a surface layer thereof, plastic flow of the cohesive laminate of the spray formed product can be stably and repeatedly caused, and thus the desired surface property can be obtained, which is preferable.

[0119] Besides transporting and processing in the order illustrated along the transport path in FIG. 16, formed product, processed product, and processing dies may be appropriately moved. For example, when a processed product is released from the die and removed, the processed product can be moved to the preheating and temperature equalizing unit, and the ultraquenching transition control injection forming can be performed again, and so on.

[0120] Note that, although illustrated as a transport device having a racetrack-shaped transport path, a transport device having a transport path of various shapes such as a linear shape or an annular shape may be used depending on restrictions such as installation space of the facility.

REFERENCE SIGNS LIST

[0121] 1 Powder supply pipe [0122] 2 Mist ejection nozzle [0123] 3 Mist ejection port [0124] 4 Inert gas ejection port [0125] 5 Flame vent [0126] 6 Powder ejection port [0127] 7 Payoff reel [0128] 8 Thin sheet substrate preheater [0129] 9 Leveler [0130] 10 Heating and equalizing device [0131] 11 Ultraquenching transition control injector [0132] 12 Rolling mill [0133] 13 Coil winder [0134] 14 Released thin sheet [0135] 15 Hoop [0136] 16 Forming die