WO2008062815A1

WO2008062815A1 - Metallic member, process for producing the same, and method of using the same

Info

Publication number: WO2008062815A1
Application number: PCT/JP2007/072511
Authority: WO
Inventors: Kiichirou Sumi; Seihachirou Ootake; Shouji Usuda
Original assignee: Ssjapan Ltd.; T.N.G. Technologies Co., Ltd.
Priority date: 2006-11-24
Filing date: 2007-11-21
Publication date: 2008-05-29

Abstract

A metallic member having excellent applicability is provided. Even when used in a room where ultraviolet irradiation is limited or in a dark place as in a shoes box, the metallic member performs a catalytic function to heighten the effects of, e.g., purifying, sterilizing, or deodorizing water or air, preventing water or air from being fouled, maintaining the freshness of foods, preventing oil deterioration, and reducing the amount of petroleum fuel to be used. The metallic member does not suffer the decrease in catalytic activity caused by oxide-layer shedding and hence has excellent long-term stability. Furthermore, it can be used in places where inclusion of metal powder, dust, or the like is problematic, as in, e.g., factories for producing semiconductors, foods, and motor vehicles and in apparatuses such as combustion apparatuses, e.g., boilers and kerosene space heaters. The metallic member (1) comprises a base (2) made of metal and, formed on the surface of the base (2), an oxide layer (4) formed by thermal oxidation comprising a noncrystalline oxide and crystalline oxide each having catalytic activity.

Description

Specification

Metal member, method for producing the same, and method for using the same

Technical field

[0001] The present invention provides water and air purification, sterilization, deodorization, antifouling, food freshness preservation and oil deterioration prevention.

The present invention relates to a metal member having catalytic activity that is effectively used for reducing the amount of petroleum fuel used, a manufacturing method thereof, and a usage method thereof.

Background art

Conventionally, metal oxides such as TiO, ZnO, WO and Fe 2 O have been used as photocatalytic materials such as water and

2 3 2 3

Widely used in applications such as air purification, sterilization, deodorization, and antifouling. Such a photocatalyst material is usually used in a powder form.

However, powdery materials have drawbacks such as being difficult to handle and recovering, such as being easily scattered and difficult to aggregate and disperse, so the photocatalytic material can be fixed to the substrate or the surface of the substrate can be oxidized. Techniques for forming metal oxide layers have been developed.

As such conventional technology, (Patent Document 1) states that “a powder of titanium or a titanium alloy is sprayed onto the surface of a base material made of titanium or a titanium alloy, and a titanium oxide film is coated on the surface of the substrate. "A photocatalytic coating composition" is disclosed.

(Patent Document 2) states that, after anodizing a titanium-based alloy base material, heat treatment is performed in an oxidizing atmosphere at a temperature range of 300 to 800 ° C, more preferably 400 to 700 ° C. A process for producing oxidized titanium having photocatalytic activity for forming an oxide layer on the surface of a material is disclosed.

Patent Document 1: JP 2002-316056 A

Patent Document 2: JP-A-8-246192

Disclosure of the invention

Problems to be solved by the invention

[0003] However, the above conventional techniques have the following problems.

(1) In the technique disclosed in (Patent Document 1), by spraying titanium or titanium alloy powder onto the surface of the base material, the titanium or titanium alloy powder is melted and adhered to the surface of the base material. More The outermost surface of the film melted and adhered to the surface is oxidized to form a titanium oxide film, but the bonding strength between the titanium and titanium alloy powder melted and adhered to the surface of the substrate and the substrate is small! Therefore, there is a problem that the photocatalytic activity may drop due to the molten deposit falling off during use! In addition, it can be used as a daily necessities, but because molten deposits may fall off during use, burning of semiconductors, foods, automobiles, boilers, oil stoves, etc. where metal powder or dust is a problem is a problem. There was a problem that the use was limited in factories and in factories. Further, titanium or titanium alloy powder has a problem that it may explode if it is easily flammable at high temperatures. In addition, the sprayed powder adheres to the interior of the injection device where the base material alone is placed, the chamber where the base material is placed, etc., so that the efficiency is poor and the cleaning work requires a lot of labor and lacks productivity. Had problems.

(2) The spray powder is sprayed onto the base material from a nozzle with a diameter of about 9 mm, and the surface of the base material sprayed with the spray powder reaches a high temperature at which the spray powder melts locally. There are significant temperature spots where the body is colliding and where it is not. For this reason, when sprayed powder is sprayed onto a large-area plate-shaped substrate and the coating process is performed, the substrate deforms significantly due to temperature spots and twists or curls. It is difficult to do this, and it is necessary to constrain the shape with a mold or the like, or to remove the deformation by annealing or the like!

(3) The technique disclosed in (Patent Document 2) forms an oxide film on a titanium-based alloy base material by anodic oxidation. The principle of anodic oxidation is that the surface of the titanium-based alloy substrate of the anode is oxidized to form an oxide film, and metal ions move to the surface of the oxide film by an electric field, so that oxygen and oxygen are formed on the surface of the oxide film. Bonding causes oxidation to proceed. The oxide film formed by this reason anode oxidation, the literature; as described in (Kobe Steel Technical _{Report, Vol.49, N 0 .3 65-67 (} De C .1999)), anatase type titanium oxide It is formed. Anatase-type titanium oxide has a photocatalytic action under ultraviolet light (light with a wavelength of 400 nm or less) and exhibits antibacterial properties and the ability to decompose organic substances, odors and odorous substances, but indoors and shoeboxes with low UV irradiation These abilities are rarely demonstrated in some places in the country. For this reason, in order to demonstrate the ability in indoor places, an ultraviolet lamp that irradiates light to anatase titanium oxide, A light source such as a black light is required, and a power source is required.

(4) In anodic oxidation, oxidation progresses on the surface of the oxide film, and therefore, due to its nature, the oxide film has a problem of being easily peeled off from the base material.

(5) After anodizing the titanium-based alloy base material, when heat treatment occurs at a high temperature of 700 to 800 ° C in an oxidizing atmosphere, especially when the base material has a large area and a plate shape In this case, the substrate is significantly deformed by temperature spots and twisted or rounded, so it is difficult to maintain the desired shape. The shape is constrained by a formwork or the like, and annealing is performed to remove the deformation. There is a problem that it is complicated and needs to be removed!

[0004] The present invention solves the above-described conventional problems, and exhibits catalytic action even in a room or a shoebox where the amount of ultraviolet light irradiation is small, thereby purifying, sterilizing, deodorizing and preventing water and air. It is possible to increase the effect of soiling, keeping food fresh, preventing oil deterioration, reducing the amount of petroleum fuel used, etc. To provide a metal member with excellent applicability that can be used in factories and equipment such as semiconductors, foods, automobiles, boilers, oil stoves, etc. And

In addition, the present invention also provides water and air purification, sterilization, deodorization, antifouling, food freshness preservation and oil deterioration prevention even in indoor places where the amount of ultraviolet irradiation is low, in shoeboxes and fuel tanks. The objective is to provide a method for manufacturing metal parts that can produce the effect of reducing the amount of petroleum fuel used.

In addition, the present invention provides antibacterial properties, the effect of decomposing organic substances and offensive odors, maintaining the freshness of foods, preventing the deterioration of oil, and reducing the amount of oil used. To provide a method of using a metal member that can be surely exhibited in a certain place.

Means for solving the problem

[0005] In order to solve the above-described conventional problems, the metal member and the manufacturing method thereof of the present invention have the following configurations.

The metal member according to claim 1 of the present invention includes a metal base material and a heat applied to the surface of the base material. It has a structure including an amorphous oxide having catalytic activity formed by oxidation and an oxide layer containing a crystalline oxide.

With this configuration, the following effects can be obtained.

(1) It has an oxide layer containing a catalytically active amorphous oxide and a crystalline oxide formed by thermal oxidation on the surface of the substrate! There are few! / And it is possible to demonstrate antibacterial properties and the ability to decompose organic substances and offensive odorous substances even in places such as indoors and shoeboxes. This is presumed as follows. That is, an oxide layer formed on the surface of a metal base material by thermal oxidation under predetermined conditions is mostly an amorphous oxide because oxidation proceeds by diffusion of oxygen into the base material. Some crystalline oxides are mixed. When an interface between an amorphous oxide and a crystalline oxide exists, an interface state is formed, and a narrow forbidden energy band different from the forbidden energy band of an amorphous oxide or a crystalline oxide is formed. Formed at the interface. For this reason, even if ultraviolet rays are not irradiated, the electrons are excited in the valence band conduction band and the catalytic activity is exhibited only by applying a slight amount of heat energy such as the energy gap of the interface.

(2) The oxide layer formed on the surface of the base material by thermal oxidation has extremely stable physical properties, and is formed continuously without a clear interface between the base material and the oxygen-deficient layer / monooxide layer. The catalytic action does not decrease due to the falling off of the chemical layer, and the durability is excellent.

(3) Since various colors appear due to the light interference phenomenon caused by the oxide layer, a variety of colors can be obtained, and it is possible to obtain a decorative effect.

[0006] Here, as the material of the metal base material, titanium, silver, tin, copper, platinum, gold, molybdenum, vanadium, aluminum, etc., titanium alloy, which is an alloy of titanium, tin, copper, silicon, What was formed with materials, such as zinc and tungsten, is used. Semiconductors that oxidize these metals generate electrons and holes when irradiated with light with energy greater than the band gap, and react with water, oxygen, etc. to generate OH radicals, superoxide anions, etc. Has catalytic activity.

[0007] As the shape of the substrate, those formed into a plate shape, a foil shape, a granular shape, a rod shape, a linear shape, a net shape, a lath net shape, a non-woven fabric, a cylindrical shape, a tape shape, and the like are used.

In addition, it is preferable that the base material is formed into a plate shape, a foil shape, a tape shape, or a granular shape. Since the surface area per unit weight can be increased, the contact area per unit weight with liquids and gases is widened, resulting in excellent cost performance, as well as water and air purification, sterilization, deodorization, antifouling, and The power S can be used to increase the effects of maintaining freshness, preventing oil deterioration, and reducing the amount of petroleum fuel used.

The thickness of the plate-like, foil-like or tape-like substrate is preferably 20 m to 1 mm. A metal member formed of a foil-like tape-like base material can be used as a freshness-keeping agent by sticking to the inner surface of a medical product or food packaging material or food packaging. As the substrate thickness becomes thinner than 20 m, the productivity of the substrate decreases, and as it becomes thicker than 1 mm, the thickness of the substrate increases with respect to the thickness of the oxide layer. There is a tendency for the cost of the base material to increase and the cost effectiveness to decrease.

As the diameter of the granular base material, 0.3 to 30 mm is preferably used. As the diameter becomes smaller than 0.3 mm, it tends to be scattered and difficult to handle and collect, and when it becomes larger than 30 mm, the specific surface area becomes smaller. Since the cost of the base material with respect to the catalytic activity effect that can be increased tends to increase and the cost effectiveness tends to decrease, neither is preferable.

[0008] As a method of thermally oxidizing the substrate, a method of heating the substrate, a method of supplying an oxidizing species such as water vapor to the surface of the substrate, and the like can be used. These can be performed at a pressure approximately equal to atmospheric pressure (atmospheric pressure oxidation). It can also be carried out under pressure (high pressure oxidation) or under reduced pressure (low pressure oxidation). In addition, the oxidation species can be diluted with an inert gas or the like (diluted oxidation).

In addition, it does not directly heat the substrate or supply oxidizing species, but it applies pressure or striking force to the substrate with a hammer or press, as in forging processes such as coining and embossing, and tensile force. For example, it is possible to use a method of oxidizing the base material by plastic deformation and generating plastic deformation frictional heat. Further, a method of heating the base material, a method of supplying an oxidizing species such as water vapor to the surface of the base material, and a method of plastically deforming the base material to generate plastic deformation frictional heat can be used in combination.

[0009] As the amorphous oxide and the crystalline oxide, those formed in an oxide layer thermally oxidized under specific conditions are used. If the substrate is made of titanium or titanium alloy, the crystallinity It is presumed that the oxide is anatase type titanium oxide. This is because the thermal oxidation conditions are mild.

As the heating temperature of the substrate in the thermal oxidation, 200 to 450 ° C, preferably 200 to 400 ° C is suitably used in the atmospheric pressure. As the heating temperature is lower than 200 ° C and higher than 400 ° C, the ability to decompose organic substances, offensive odors and offensive odors decreases in places such as indoors and shoeboxes where the amount of UV irradiation is low. There is a tendency to Particularly when the temperature is higher than 450 ° C., this tendency becomes remarkable. The reason for this is not clear, but it is assumed that the structure and ratio of amorphous oxide and crystalline oxide in the oxide layer change and the energy gap at the interface increases. /!

In a pressurized state or a reduced pressure state, heating can be performed under a temperature condition corresponding to 200 to 450 ° C. under normal pressure.

The heating time is preferably a force depending on the size of the substrate;! To 60 minutes. This is because even if the heating time is short or long, the antibacterial effect in a room or in a shoebox is reduced. In the case of high pressure oxidation, since the oxidation rate is fast, the heating time can be shortened.

As heating conditions, it is preferable to rapidly heat the substrate. As a specific method, for example, a method in which a normal temperature base material is put into a heating furnace maintained at 200 to 450 ° C. is used. After placing the base material in the heating furnace, when the heating furnace is heated to 200-450 ° C and the base material is heated to form an oxide layer, the amount of UV irradiation is small! This is because the catalytic effect at this point became poor. By heating the substrate rapidly, non-uniform thermal stress is applied to the substrate, resulting in the formation of a narrow forbidden energy zone at the interface between the amorphous oxide and the crystalline oxide in the oxide layer. I guess it is because the probability of being done increases! /!

[0010] An antibacterial thin film layer such as silver or platinum can be formed on a part or the entire surface of the oxide layer by vapor deposition or the like. As a result, the antibacterial properties can be enhanced, and the ability to disinfect Escherichia coli, mold, etc. can be enhanced.

[0011] The metal member according to claim 2 of the present invention has a metal base material in which a plurality of permanent strain portions are formed in response to an external force and a catalytic activity in which the surface of the permanent strain portions is oxidized. And an oxide layer. With this configuration, the following effects can be obtained.

(1) The surface of the permanent strained portion is immediately oxidized by the plastic deformation frictional heat (heat generated by internal friction) generated when the permanent strained portion is formed by plastic deformation, and an oxide layer is formed. Most of the oxidized layers oxidized in a short time are amorphous oxides and mixed with crystalline oxides, so they are antibacterial even in places such as indoors and shoeboxes where the amount of UV irradiation is low. , It can demonstrate the ability to decompose organic substances and off-flavors. The inferred mechanism is the same as in claim 1 and will not be described.

(2) Since the surface of the permanent strain portion formed on the base material is provided with an oxidized layer! /, The permanent strain portion is work hardened, so the rigidity of the base material is increased and the base material is deformed. The force S can be obtained to obtain a metal member having a large area and a long catalytic activity without deformation such as twisting and warping.

(3) Permanently strained parts are formed at multiple locations on the substrate! /, So the surface area can be increased compared to a planar substrate, and the contact area with water, oil, and air is increased. Therefore, water and air purification, sterilization, deodorization, antifouling, maintaining the freshness of food, preventing oil deterioration, and reducing oil fuel consumption can be enhanced.

(4) The oxide layer formed on the surface of the base material has extremely stable physical properties and is formed continuously without a clear interface between the base material and the oxygen-deficient layer or the mono-oxide layer. Therefore, the catalytic action is not lowered and the durability is excellent.

(5) Since the permanent strain portion can be formed mechanically, it has excellent productivity and production stability.

[0012] Here, the base material is the same as that described in claim 1, and the description thereof is omitted. As described above, an antibacterial thin film layer can be formed on the surface of the oxide layer.

[0013] Permanently strained portions are locations where a plurality of portions of the base material are plastically deformed by an applied external force, and are distributed over substantially the entire surface of the base material with appropriate intervals.

Examples of the external force applied to the base material include pressure and striking force applied by a hammer press such as forging processes such as coining and embossing. In addition, the tensile force can be raised. In the case of applying a tensile force, particularly in the case of a plate-like base material, by forming a cut portion or a hole in the base material and applying a tensile force from both ends, the periphery of the cut portion or the hole portion can be applied. While forming a permanent strain part in a surrounding, a cut | interruption part and a hole part can be expanded. Thereby, liquid permeability and air permeability can be imparted to the substrate.

[0014] The pitch of the permanent strain portions formed at a plurality of locations of the substrate is preferably 1 to 20 mm. As the pitch force of the permanent strain portion becomes smaller than mm, the size of each permanent strain becomes smaller and it becomes difficult to work and harden, and the rigidity of the base material tends to be difficult to improve. Since permanent strained parts will be scattered, when the base material is heated for the purpose of forming an oxide layer after the permanent strained part is formed, the base material is likely to twist or warp between the permanent strained parts. Neither is desirable because there is a trend.

When a plate-like base material is used, the concavo-convex portion can be formed as a permanent strain portion by a forging process such as coining or embossing. As a result, the uneven portions are work hardened to increase the rigidity of the base material, and the surface of the uneven portions is immediately oxidized by the plastic deformation frictional heat (heat generated by internal friction) generated in each uneven portion during processing to form an oxide layer. Is done. This makes it possible to exhibit antibacterial properties and the ability to decompose organic substances and odorous and offensive odor substances even in indoor places where the amount of UV irradiation is small or in a shoebox.

[0016] As the concavo-convex portion, a pyramid shape such as a quadrangular pyramid or a cone, a truncated pyramid shape such as a truncated quadrangular pyramid or a truncated cone, a convex or concave portion such as a hemispherical shape, a wavy shape, or a line shape is provided in the vertical and horizontal directions. Or those arranged in an oblique direction are used. When a concave portion is formed on one side by deforming a plate-like base material, since this concave portion is a convex portion when viewed from the opposite side, an uneven portion is formed on the surface of the base material.

It is desirable that the concavo-convex portion is formed in a plane symmetry or a point symmetry on the base material by forging. This is because the uneven portions can be arranged regularly and evenly, the force S can be increased uniformly and the substrate can be prevented from warping and twisting.

[0017] The depth of the concave portion in the concave and convex portion is preferably 0.2 to 5 mm as the height of the convex portion. As the depth and height of the concavo-convex part becomes smaller than 0.2 mm, the plastic deformation frictional heat generated due to the small plastic deformation amount in each concavo-convex part is poor, so the oxide layer is thin and the deformation is small, so work hardening The base material is less rigid, and when the base material is further heated to form an oxide layer, the base material tends to be twisted or warped. Due to the force S and the formation of uneven parts tends to be difficult Neither is preferred.

[0018] When a plate-like base material is used, a plurality of cut portions or holes formed in the base material can be formed around the cut portions or the holes by receiving a tensile force as the permanent strain portion. . As a result, the permanent strained portion is work-hardened to increase the rigidity of the base material, and the cut portion and the hole portion are widened, so that the base material can be made into a net and liquid permeability can be imparted.

[0019] The cut portion is formed so as to be substantially orthogonal to the tensile direction applied to the substrate. This is because the periphery of the cut portion is plastically deformed by a tensile force to widen the cut portion. The hole is formed in an oval shape, an oval shape, a rectangular shape, or the like, and the hole is used in which the major axis direction of the hole portion is arranged substantially orthogonal to the tensile direction applied to the substrate. This is because the hole is widened by plastically deforming the periphery of both ends in the minor axis direction of the hole by a tensile force.

[0020] As the length of the cut portion and the length of the long diameter of the hole portion, 5 to 20 mm is preferably used.

As the length becomes shorter than 5 mm, the deformation amount of the permanent strain portion decreases, and the work hardening tends to be poor and the rigidity of the base material tends to decrease.As the length becomes longer than 20 mm, the permanent strain portions that are work hardened are scattered. For this reason, when the base material is further heated to form an oxide layer, it tends to be twisted or warped between the permanently strained portions.

[0021] The invention according to claim 3 of the present invention is the metal member according to claim 1, wherein the base material is made of titanium or a titanium alloy.

With this configuration, in addition to the operation obtained in claim 1, the following operation can be obtained.

(1) Titanium or titanium alloy is tough despite its low specific gravity, strong against acids and alkalis, excellent in corrosion resistance, hydrophilic and non-magnetic, and difficult to cause metal allergies. Applicable and excellent in applicability.

(2) The oxide layer of titanium oxide formed by thermally oxidizing the surface of titanium or titanium alloy is

In addition, it has excellent durability without photodissolving, and because the energy required to develop catalytic activity is small, it can exhibit catalytic activity similar to photocatalyst even in places where no light is irradiated. Excellent.

Here, as titanium, pure titanium such as JIS 1 to 4 can be used. Titanium alloy For example, it is possible to use Ti-3A1-2-5V, Ti-6A1-4V, Ti-15V-3Cr-3Sn-3A1, and the like. Among these, JIS type 1 pure titanium is preferably used. This is because the purity of titanium is high and the elongation is large, so that the moldability of the permanent strain portion is excellent, and the higher the purity of titanium is, the more difficult it is to have adverse effects such as allergies on the human body!

[0023] The invention according to claim 4 of the present invention is the metal member according to claim 2, wherein the base material is made of titanium or a titanium alloy.

With this configuration, in addition to the operation obtained in claim 2, the following operation can be obtained.

[0024] Since titanium and titanium alloys are described in claim 3, their description is omitted here.

[0025] In the method for producing a metal member according to claim 5 of the present invention, the metal substrate is heated to a temperature of 200 to 450 ° C under normal pressure, and / or the surface of the metal substrate is heated. It has a configuration including an oxide layer forming step of forming an oxide layer having catalytic activity by oxidizing the surface of the base material by forming permanent strain portions at a plurality of locations.

With this configuration, the following effects can be obtained.

(1) Since an oxide layer forming step is provided, a metal base material is heated to a temperature of 200 to 450 ° C under normal pressure, or a permanent strain portion is formed by plastic deformation to generate plastic deformation frictional heat (internal friction). Heat generation), the surface of the base material can be oxidized to form a catalytically active oxide layer, and indoors where there is little UV irradiation, in shoeboxes, fuel tanks, and other places, Water and air purification, sterilization, deodorization, antifouling, maintaining the freshness of food, preventing oil deterioration, and reducing the amount of petroleum fuel used can be achieved.

[0026] Here, the base material, the heating temperature, and the permanent strain portion are the same as those described in claim 1 or 2, and thus the description thereof is omitted. [0027] In the oxide layer forming step, (1) an operation of heating a metal substrate to a temperature of 200 to 450 ° C under normal pressure, (2) permanent strain at a plurality of locations on the surface of the metal substrate. Forming a part! Force that can form an oxide layer having catalytic activity even if the operation is shifted! / Permanently strained While forming a part, it can be heated to 200-450 ° C at the same time. In addition, the permanent strain portion can be formed after heating, or the permanent strain portion can be heated after forming.

[0028] Furthermore, the plate-like base material on which the permanent strain portion is formed can be plastically deformed across a plurality of locations of the permanent strain portion by the secondary forming step. Due to the secondary forming process, it can be formed into any shape according to the application by bending, drawing, etc., and it has excellent flexibility.

[0029] Here, as the secondary forming step, a bending calorie such as die bending, bending, and roll forming, and press working such as drawing are performed in a range wider than the size of each permanent strain portion. A material that plastically deforms the material is used.

In the secondary molding process, it is desirable to perform molding while heating the substrate to 200 to 450 ° C! /. This is because the surface hardness is increased and the deformation resistance is large at the permanent strain part, so that the spring back in the secondary forming is reduced by heating. As the heating temperature of the base material becomes lower than 200 ° C, the springback amount of the base material tends to increase and it becomes difficult to form into any shape. Since there is a tendency for the catalyst activity to decrease, neither is preferable.

[0030] The invention according to claim 6 of the present invention is the method for producing a metal member according to claim 5, wherein the base material is formed in a plate shape, foil shape, or tape shape, and the permanent strain portion. However, it has a configuration that is an uneven part that is forged with a hammer between two dies having uneven parts formed on the surface so as to mate with each other.

With this configuration, in addition to the operation obtained in claim 5, the following operation can be obtained. (1) Since the permanent strain portion is an uneven portion forged with a die or a hammer, the uneven portion is processed and hardened to increase the rigidity of the base material, and plastic deformation that occurs in each uneven portion during processing. As a result, the surface of the surface is immediately oxidized and a catalytically active oxide layer can be formed. It can produce effects such as air purification, sterilization, deodorization, antifouling, keeping food fresh, preventing oil deterioration, and reducing the amount of petroleum fuel used.

Here, as the concavo-convex portion, those formed on a plate-like, foil-like or tape-like substrate by plastic working (forging) such as coining or embossing are used. Inserting the base material between the upper and lower molds with irregularities and pressing the base material with the upper and lower molds moving up and down to form irregularities intermittently, with concave or convex The base is pressed with a lower mold that is convex or concave so as to fit into the upper mold and the concave / convex portions are intermittently formed, or the base between two mold rollers with irregularities formed. The substrate is pressed between rotating mold rollers to continuously form irregularities, and the substrate is placed on a table with a recess or hole and hit with a hammer to remove the irregularities. What is to be formed can be used. When the uneven portion is formed in the atmosphere using such means, the uneven portion is oxidized by the plastic deformation friction heat on the top and bottom of the uneven portion, the inclined surface portion to be squeezed, etc., and an oxidized layer is formed. Since the surface hardness of the base material increases, the rigidity and elasticity of the base material can be increased more than simply processing into a corrugated plate by bending or the like for the purpose of increasing the rigidity.

Further, when forming the concavo-convex part, the concavo-convex part can be formed under heating conditions by heating the upper mold, the lower mold, the mold roller, the base material and the like. As a result, the thickness of the oxide layer formed by the plastic deformation frictional heat can be increased, whereby the rigidity of the substrate can be further increased and the catalytic activity can be increased. Note that when forming the concavo-convex portion, the temperature of the substrate to be heated is preferably 450 ° C. or less. This is because when the heating temperature exceeds 450 ° C, the antibacterial properties and the ability to decompose organic substances and offensive odorous substances tend to be reduced in places such as indoors and in shoeboxes where the amount of UV irradiation is small.

By forming the protrusions formed on the upper mold, lower mold, mold roller, etc. in a pointed shape, it is possible to form a through-hole part by drilling at the same time as forming the uneven part on the substrate. Thus, water permeability can be imparted to the substrate.

[0032] The method for producing a metal member according to claim 7 of the present invention includes the metal member according to any one of 1 to 4 or the metal member produced by the method according to claim 5 or 6 in a liquid. The liquid is brought into contact with a gas under weak excitation light with a UV irradiation amount of less than 0. OlW / m ² or in a certain place while being immersed in the gas. With this configuration, the following effects can be obtained.

(1) The metal member of the present invention has antibacterial properties even in places where the amount of ultraviolet irradiation is small, such as indoors and in shoeboxes, decomposition effects of organic substances and offensive odors, preservation of food freshness, prevention of oil deterioration, The effect of reducing the amount of petroleum fuel used can be exhibited, but the effect can be further enhanced by bringing the gas into contact with the gas while immersed in a liquid. Although the mechanism has not been elucidated, it has been confirmed that when the metal member of the present invention is immersed in a liquid and left in place, the cluster of the liquid molecules becomes small and the molecular vibration and rotation change. Inferred to have some effect.

[0033] Here, the liquid into which the metal member is immersed includes water, gasoline, heavy oil, light oil, kerosene, and other fossil fuel processed products such as lubricating oil and insulating oil, and fossil fuel substitutes such as alcohol fuel. And edible oils such as salad oil and sky oil.

Examples of the gas include air and exhaust gas.

[0034] As the excitation light, sunlight, ultraviolet rays, or the like can be used. Even when the amount of ultraviolet irradiation is small, the metal member of the present invention exhibits antibacterial properties, decomposition effects of organic substances and offensive odors, etc., but when the ultraviolet irradiation amount exceeds 0. OlW / m ² Even with a photocatalyst using titanium dioxide or the like, the effect of decomposition of the metal member of the present invention is lost because the decomposition effect is similarly exhibited.

The invention's effect

[0035] As described above, according to the metal member and the manufacturing method thereof of the present invention, the following advantageous effects can be obtained.

According to the invention of claim 1,

(1) It has an oxide layer containing a catalytically active amorphous oxide and a crystalline oxide formed by thermal oxidation on the surface of the substrate! /, So narrow! /, Forbidden An energy band is formed at the interface between the amorphous oxide and the crystalline oxide, and electrons are excited from the valence band to the conduction band by applying a small amount of energy that exceeds the energy gap of the interface. It is possible to provide metal members that exhibit catalytic functions such as antibacterial properties, the ability to decompose organic substances and offensive odors, and odorous substances even in places such as indoors and shoeboxes where there is little irradiation.

(2) The physical properties of the oxide layer formed by thermal oxidation are extremely stable. In the factory and equipment such as semiconductors, foods, automobiles, boilers, oil stoves, and other combustion equipment where the catalyst action does not decrease due to dropping and is excellent in stability over time, and mixing of metal powder and dust is a problem. It is possible to provide a metal member that can be used internally and has excellent applicability.

(3) Since various colors appear due to the light interference phenomenon caused by the oxide layer, it is possible to obtain various color tones and to provide a metal member having a catalytic activity with excellent decorativeness.

[0036] According to the invention of claim 2,

(1) The surface of the permanent strained part is immediately oxidized by the plastic deformation frictional heat (heat generated by internal friction) generated when the permanent strained part is formed by plastic deformation, and most of it is amorphous oxide. There is an oxide layer with mixed crystalline oxides, so the catalyst has antibacterial properties and the ability to decompose organic substances, offensive odors and offensive odors even in places where the amount of UV irradiation is small, such as indoors or in shoeboxes. It is possible to provide a metal member that exhibits its action.

(2) Since the surface of the permanent strain portion formed on the base material is provided with an oxidized layer! /, The permanent strain portion is work hardened, so the rigidity of the base material is increased and the base material is deformed. It is possible to provide a metal member having a large area of catalytic activity without deformation such as twisting and warping.

(3) Permanently strained parts are formed at multiple locations on the substrate! /, So the surface area can be increased compared to a planar substrate, and the contact area with water, oil, air, etc. is large. Therefore, it is possible to provide a metal member that is excellent in purification of water and air, sterilization, deodorization, antifouling, preservation of food freshness, prevention of oil deterioration, and reduction in the amount of petroleum fuel used.

(4) The physical properties of the formed oxide layer are extremely stable, the catalytic action is not reduced by dropping the oxide layer, and the stability over time is excellent, and the mixing of metal powder and dust is a problem. Therefore, it is possible to provide a metal member with excellent applicability that can be used in a field such as a combustion device such as a semiconductor, food, automobile, boiler, or petroleum stove, or in a device.

(5) Since the permanent strain portion can be mechanically formed, it is possible to provide a metal member that is excellent in productivity and excellent in production stability.

[0037] According to the invention of claim 3, in addition to the effect of claim 1,

(1) Titanium or titanium alloy is resistant to acids and alkalis, has excellent corrosion resistance, and is tough and magnetic. Furthermore, since metal allergy is unlikely to occur, it is possible to provide a metal member that can be applied to various uses and has excellent applicability.

Because it does not cause photodissolution and has excellent durability, and the energy required to develop catalytic activity is small, it exhibits catalytic activity similar to that of photocatalysts even in places where no light is irradiated, so that oil fuel reforming A metal member with excellent applicability that has the effects of reducing fuel consumption by improving the life of the product by reforming lubricants and edible oils, maintaining the freshness of food, sterilizing indoors, deodorizing, preventing slime, etc. Can be provided.

[0038] According to the invention of claim 4, in addition to the effect of claim 2,

(1) Titanium or titanium alloy is resistant to acids and alkalis, has excellent corrosion resistance, is strong and does not have magnetism, and is less likely to cause metal allergy, so that it can be applied to various uses and can provide a metal member with excellent applicability.

[0039] According to the invention of claim 5,

(1) By heating a metal base material to a temperature of 200 to 450 ° C under normal pressure, or by forming a permanent strain part by plastic deformation and generating plastic deformation frictional heat (heat generation by internal friction). The surface of the base material can be oxidized to form an oxide layer with catalytic activity. Water, air purification, sterilization, and deodorization can be performed indoors where the amount of UV irradiation is low, in shoeboxes and fuel tanks. Therefore, it is possible to provide a method for producing a metal member capable of producing antifouling, maintaining the freshness of food, preventing oil deterioration, and reducing the amount of petroleum fuel used.

[0040] According to the invention of claim 6, in addition to the effect of claim 5,

(1) Since the permanent strain part is an uneven part forged with a die or a hammer, the uneven part is work hardened to increase the rigidity of the base material, and plastic deformation that occurs in each uneven part during processing Since the surface of the irregularities is immediately oxidized by frictional heat and an oxide layer with catalytic activity can be formed, purification and sterilization of water and air can be performed in indoor places where the amount of UV irradiation is small, in places such as shoeboxes and fuel tanks. , Deodorizing, antifouling, maintaining the freshness of food, preventing oil deterioration, and reducing the amount of petroleum fuel used can be provided.

[0041] According to the invention of claim 7,

(1) Anti-bacterial properties, organic substances and off-flavors even in places with low UV irradiation, such as indoors and shoeboxes • Decomposition of malodorous substances, preservation of food freshness, prevention of oil deterioration, and reduction of oil fuel consumption Although it can be exhibited, it is possible to provide a method of using a metal member that can be further enhanced by bringing the gas into contact with the gas while being immersed in a liquid.

Brief Description of Drawings

[Fig.l] (a) Perspective view of main part of metal member in Embodiment 1 of the present invention (b) Cross-sectional view of main part of metal member

[Fig. 2] (a) Schematic diagram showing the process of forming irregularities through the substrate between the two mold rollers (irregularity formation process) (b) Schematic of the two mold rollers that are interlaced Enlarged sectional view

FIG. 3 is a perspective view of a metal member in the second embodiment.

FIG. 4 is a schematic diagram of a metal member in embodiment 3.

[Figure 5] FTIR (ATR method) wave number and absorption spectrum

[Fig.6] Spectrum showing the ratio of FTIR (ATR method) wave number and absorbance

Explanation of symbols

[0043] 1, 21 Metal member

2, 22, 25 Base material

3 Irregularities

4 Oxide layer

10 type roller

11 Shaft

12 Gear projection

13 Spacer

23 Cut 24, 26 Permanent strain section

27 Lower mold

28 Upper mold

BEST MODE FOR CARRYING OUT THE INVENTION

The best mode for carrying out the present invention will be described below with reference to the drawings.

(Embodiment 1)

FIG. 1 (a) is a perspective view of main parts of a metal member according to Embodiment 1 of the present invention, and (b) is a cross-sectional view of main parts of the metal member.

In the figure, 1 is a metal member in Embodiment 1 of the present invention, 2 is a plate-like substrate formed of titanium, zinc, tandastain, etc. to a thickness of 0.05 to lmm, 3 is a substrate 2 An uneven portion as a permanent strain portion in which frusto-convex pyramid-like convex portions and corresponding concave portions are repeatedly arranged in an embossed form on both sides, and 4 is an oxide layer in which the surface of the substrate 2 is oxidized.

A method for manufacturing the metal member according to the first embodiment of the present invention configured as described above will be described below.

Fig. 2 (a) is a schematic diagram showing a process (oxidation layer forming process) in which an uneven part is formed through a base material between two mold rollers and thermally oxidized, and (b) is interlaced FIG. 3 is a schematic enlarged cross-sectional view of two mold rollers.

In the figure, 10 is a mold roller arranged with a slight gap, 11 is a shaft of the mold roller 10, 12 is a repetitive form of irregularities consisting of a truncated quadrangular pyramidal convex part and a female concave part on the outer periphery. The formed gear convex portion 13 is an annular spacer formed with a predetermined thickness inserted between the gear convex portions 12 and 12. The gear projections 12 and the spacers 13 are alternately stacked, and the shaft 11 is passed through the center to form the mold roller 10. The two mold rollers 10 and 10 are arranged with a slight gap so that the irregularities formed on the outer periphery of the gear convex portion 12 are interleaved with each other. Has been rotated to

Yes

In the present embodiment, the mold rollers 10 and 10 are heated by a built-in heater (not shown), and the substrate 2 is heated to 200 to 450 ° C. by the mold rollers 10 and 10.

[0046] In the oxide layer forming step, when the substrate 2 is passed between the two rotating mold rollers 10 and 10, Since the unevenness formed on the outer periphery of the gear convex portion 12 of the mold rollers 10 and 10 is arranged with a slight gap so that the irregularities formed in each other, the shape of the concave and convex shape on the surface of the gear convex portion 12 The concavo-convex portions 3 corresponding to the above are formed in an embossed shape on both surfaces of the base material 2 by forging, and the base material 2 comes out between the mold rollers 10 and 10. At this time, the forged base material 2 generates plastic deformation frictional heat, and the surface is oxidized within a short time to form the oxide layer 4. In addition, since the mold rollers 10 and 10 are heated, the base material 2 is suddenly heated to 200 to 450 ° C when passing between the mold rollers 10 and 10, and this also causes the base material 2 to The surface is thermally oxidized to form an oxide layer 4.

If necessary, the front and back surfaces of the base material 2 are further thermally oxidized by heating the base material 2 on which the uneven portions 3 are formed in an oxidizing atmosphere (usually an air atmosphere) to 200 to 450 ° C under normal pressure. Thus, the oxide layer 4 can be formed on the surface of the uneven portion 3 formed on both surfaces of the base material 2.

As described above, since the metal member according to Embodiment 1 of the present invention is configured, the following operation can be obtained.

(1) Since the surface of the concavo-convex part 3 formed on the base material 2 as the permanent strain part is provided with the oxidized layer 4 that is oxidized, the concavo-convex part 3 is work hardened, so that the base material 2 has high rigidity. The base material 2 on which the layer 4 is formed can be prevented from being deformed, and the metal member 1 having a large area of catalytic activity without deformation such as twisting or warping can be obtained.

(2) The surface of the concavo-convex portion 3 is immediately thermally oxidized by the plastic deformation frictional heat (heat generation due to internal friction) generated when the concavo-convex portion 3 as a permanent strain portion is formed by plastic deformation, and an oxide layer 4 is formed. The Most of the oxide layer 4 formed by thermal oxidation for a short time is an amorphous oxide, in which a crystalline oxide is mixed, and the interface between the amorphous oxide and the crystalline oxide is present. It is surmised that a narrow forbidden energy band will be formed, so that electrons will be excited at room temperature and the UV radiation will be low in the room or in shoeboxes, etc. Can demonstrate ability.

(3) Since uneven portions 3 are formed at multiple locations on the base material 2, the surface area can be increased compared to a flat base material, and the contact area with water, oil, air, etc. is increased. Water, air purification, sterilization, deodorization, antifouling, maintaining the freshness of food, preventing oil deterioration, and reducing oil fuel consumption can be enhanced.

(4) The physical properties of oxide layer 4 formed by thermal oxidation are extremely stable. The catalyst action does not decrease due to the falling off, and the durability is excellent.

(5) Since various colors appear due to the light interference phenomenon caused by the oxide layer 4, a variety of colors can be obtained and the decorativeness is excellent.

Further, according to the method for manufacturing a metal member in the first embodiment of the present invention, the following operation is obtained.

(1) The base material 2 on which the concavo-convex portion 3 is formed as a permanent strain portion is hardened because the concavo-convex portion 3 is work-hardened and has high rigidity./ Even if it occurs, it is possible to prevent the base material 2 from being deformed, and to obtain the metal base material 1 having a large area of catalytic activity without deformation such as twisting or warping.

(2) Oxidized layer having catalytic activity by thermally oxidizing the surface of the base material 2 by forming the uneven part 3 as a permanent strain part by plastic deformation and generating plastic deformation frictional heat (heat generation due to internal friction). 4 can be formed, so it can be easily manufactured in a simple process and has excellent productivity.

(3) Since the base material 2 is passed between the two mold rollers 10 that have irregularities formed on the outer periphery so as to rub against each other, the irregularities 3 can be formed continuously and long The embossed uneven portion 3 can be easily formed on the belt-like base material 2 and is excellent in flexibility and productivity.

(4) Since the mold rollers 10 and 10 are heated and the base material 2 can be heated to 200 to 450 ° C. in addition to the plastic deformation frictional heat generated when forming the concavo-convex portion 3, thermal oxidation is performed. Thus, the oxide layer 4 can be stably formed.

(5) Since the substrate 2 that has been formed on the concave and convex portions 3 and emerges from the mold rollers 10 and 10 is further heated to 200 to 450 ° C., the oxide layer 4 can be thickened and the catalytic effect is enhanced. be able to

Yes

(6) Since the spacer 13 is inserted between the adjacent gear convex portions 12 and 12 of the mold roller 10, the base material 2 when the concave and convex portions 3 are formed by the gear convex portions 12 and 12 is provided. By reducing the applied shear force, the base material 2 can be prevented from cracking and sagging, and the metal part 1 with excellent mechanical strength can be manufactured. Wrapping around the mold roller 10 when passing! /, And / or failure can be prevented, so productivity is excellent. [0049] Here, in the present embodiment, the description has been given of the case where the truncated quadrangular pyramid-shaped uneven portion 3 is formed, but a pyramid shape such as a quadrangular pyramid and a cone, a truncated cone shape, and a hemispherical shape. In some cases, a hole is formed in the protrusion or depression of the line or the like, or the top of the protrusion or the bottom of the depression. In this case, the same effect can be obtained.

In addition, as an uneven portion forming process, the case where the substrate 2 is pressed between the rotating mold rollers 10 and 10 to continuously form the uneven portion 3 has been described. When inserting the base material 2 and pressing the base material 2 with the upper and lower molds that move up and down to form irregularities intermittently, place the base material 2 on a table with concave or hole parts and place it into a hammer. In some cases, bumps may be formed to form uneven portions.

Further, the unevenness 3 may be formed by using the force S described in the case where the mold rollers 10 and 10 are heated, and the mold rollers 10 and 10 that are not heated. Also in this case, since the plastic deformation frictional heat is generated in the base material 2 by the formation of the concavo-convex portion 3, the surface of the base material 2 can be thermally oxidized to form the oxide layer 4 having a catalytic action.

In addition, the force described in the case where the base material 2 on which the concavo-convex portion 3 is formed and comes out of the mold rollers 10 and 10 is further heated to 200 to 450 ° C. is not necessarily required. This is because the base material 2 is thermally oxidized by the plastic deformation frictional heat generated by the formation of the concavo-convex portion 3, and the oxide layer 4 having a catalytic action is formed.

[0050] (Embodiment 2)

FIG. 3 is a perspective view of a metal member in Embodiment 2 of the present invention.

In the figure, 21 is a metal member in the second embodiment, 22 is a plate-like substrate formed of titanium, zinc, tungsten or the like to a thickness of 0.05 to lmm, and 23 is suitable for substantially the entire surface of the substrate 22. A plurality of staggered cuts each having a length of 5 to 20 mm with a gap between each other, and 24 undergoes plastic deformation by receiving a tensile force in a direction substantially perpendicular to the length direction of the cut 23. The permanent strain portion is formed around the cut portion 23, and the surface of the permanent strain portion 24 is thermally oxidized to form an oxide layer having catalytic activity.

In the manufacturing method of the metal member according to the second embodiment configured as described above, after forming the cut portion 23 in the base material 22, a tensile force is applied to the base material 22 in a direction substantially orthogonal to the length direction of the cut portion 23. Then, the periphery of the cut portion 23 is plastically deformed to form a permanent strain portion 24. Then, the substrate 22 may be heated to 200 to 450 ° C. under normal pressure to thermally oxidize the surface.

If the order of the permanent strained portion 24 and the step of thermal oxidation are interchanged, and the base 22 is thermally oxidized and then the periphery of the cut portion 23 is plastically deformed to form the permanent strained portion 24, the base 22 This is not preferable because the base material 22 may be deformed by heat spots when the material is thermally oxidized, or the thermally oxidized base material 22 may be hardened and difficult to plastically deform.

[0051] As described above, since the metal member in the second embodiment is configured, in addition to the operation described in the first embodiment, the following operation can be obtained.

(1) Since the plurality of cut portions 23 formed on the base material 22 are formed around the cut portions 23 due to the tensile force, the permanent strain portion 24 is work-hardened to form the base material 22 As the rigidity of the substrate increases, the cut portion 23 is widened, so that the base material 22 can be formed into a net-like shape, and liquid permeability and air permeability can be imparted.

[0052] Further, according to the method for manufacturing a metal member in the second embodiment, the following operation is obtained in addition to the operation described in the first embodiment.

(1) Since the permanent strain portion 24 is formed around the cut portion 23 by applying a tensile force to the base material 22 having a plurality of cut portions 23, the permanent strain portion is work-hardened and the rigidity of the base material is obtained. In addition, since the cut portion 23 is widened, the base material 22 can be formed into a net shape and liquid permeability can be imparted.

Here, in the present embodiment, the case where the cut portion 23 is formed in the base material 22 has been described, but instead of the cut portion 23, hole portions such as an oval shape, a rectangular shape, and a slit shape are provided. May form. In this case as well, since a permanent strain portion can be formed by applying a tensile force in a direction substantially perpendicular to the major axis direction of the hole portion and plastically deforming the periphery of the hole portion, the same action can be obtained.

[Embodiment 3]

FIG. 4 is a schematic view of a metal member in the third embodiment.

In the figure, 25 is made of titanium, zinc, tungsten, etc., 0.05 to 0.05; a plate-like substrate formed to a thickness of 1 mm, and 26 is a pressure or striking force applied to the surface of the substrate by a hammer or a press. Permanently strained part formed in a convex shape such as hemisphere, 27 is the size of each permanently strained part 26 A lower mold in which a spherical recess wider than the upper die is formed, and 28 is an upper mold in which a spherical tip is formed.

The metal member according to the third embodiment configured as described above is configured such that the base material 25 on which the permanent strain portion 26 is formed is placed on the lower die 27 and then pressed by the upper die 28 to It can be manufactured by plastic deformation over a plurality of locations (secondary forming step). In the present embodiment, the lower mold 27 and the upper mold 28 are heated and plastically deformed while heating the base material 25 to 200 to 450 ° C.

[0055] According to the method for manufacturing a metal member in the third embodiment as described above, the following operation is obtained in addition to the operation described in the first embodiment.

(1) Since it is equipped with a secondary forming process that plastically deforms across multiple locations of the permanent strain section 26, the ability to form the base material 25 into any shape according to the application by bending, drawing, etc. It is possible and excellent in flexibility.

(2) Although the surface hardness is increased and the deformation resistance is large in the permanent strain portion 26, the base material 25 is plastically deformed while being heated to 200 to 450 ° C in the secondary forming process. Therefore, the metal member having a desired shape can be obtained.

[0056] Here, in the present embodiment, the case where the base material 25 is deformed into a spherical shape using a mold has been described. However, the present invention is not limited to this shape and processing method. V bending and U bending Various processing methods such as die bending such as end bending, bending, roll forming and drawing can be used. Further, as long as it is deformed across a plurality of locations of the permanent strain portion 26, it can be formed into an arbitrary shape.

Example

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples.

(Experiment 1)

Using a concavo-convex imparting device that forms a concavo-convex portion by pressing it with two mold rollers on a plate-like substrate formed of pure titanium (JIS type 1) 17 cm long, 10 cm wide and 0.1 mm thick Convex and concave portions as a square pyramid-shaped permanent strain portion with a convex pitch of 5 mm and a convex height of 1 mm The metal member of Experimental Example 1 was obtained.

The mold roller of the unevenness imparting device was heated, and the substrate was heated to 200 ° C. in an air atmosphere at the same time as forming the uneven portion. In addition, the rotational speed of the mold roller was adjusted so that the speed force m / s of the substrate moved by being pressed by the mold roller was achieved. The obtained metal member remained flat without being twisted or warped after being heated to 200 ° C.

(Experiment 2)

In the same manner as in Experimental Example 1, the substrate was heated to 200 ° C. with an unevenness imparting device to form an uneven portion, and the substrate taken out from the unevenness imparting device was once cooled. Next, the base material was charged into an electric furnace preheated to 350 ° C. and heated in the atmosphere for 30 minutes, and then the base material was taken out of the electric furnace and cooled, whereby the metal member of Experimental Example 2 was cooled. Got. The obtained metal member remained flat without being twisted or warped even after being heated to 350 ° C.

(Experiment 3)

The substrate is heated to 200 ° C with an unevenness imparting device to form an uneven portion, and the substrate is once cooled.Next, the substrate is charged into an electric furnace heated to 450 ° C in advance and placed in an air atmosphere. After heating for 30 minutes, a metal member of Experimental Example 3 was obtained in the same manner as in Experimental Example 2, except that the substrate was taken out of the electric furnace and cooled. The obtained metal member remained flat without being twisted or warped even after being heated to 450 ° C.

(Experimental example 4)

The substrate is heated to 200 ° C with an unevenness forming device to form an uneven portion, and the substrate is once cooled.Next, the substrate is charged into an electric furnace that has been heated to 500 ° C in advance and placed in an air atmosphere. After heating for 30 minutes, a metal member of Experimental Example 4 was obtained in the same manner as in Experimental Example 2 except that the substrate was taken out of the electric furnace and cooled. The obtained metal member remained flat without being twisted or warped even after being heated to 500 ° C.

(Experimental example 5)

A metal member of Experimental Example 5 was obtained in the same manner as in Experimental Example 1 except that the mold roller was not heated (the base material was not heated) when the uneven part was formed on the base material with the unevenness imparting device.

(Experimental example 6)

A plate-like base material made of pure titanium (JIS Class 1) with a length of 17cm, width 10cm, and thickness 0.1mm. Then, it was charged in an electric furnace preheated to 300 ° C., heated in the air atmosphere for 30 minutes, and then taken out from the electric furnace to obtain a metal member of Experimental Example 6.

The obtained metal member was twisted and warped after being heated to 300 ° C and partially deformed.

(Experimental example 7)

A plate-like base material made of pure titanium (JIS Class 1) 17 cm long, 10 cm wide and 0.1 mm thick was placed in an electric furnace preheated to 150 ° C and placed in an air atmosphere. After heating for a minute, it was taken out from the electric furnace to obtain a metal member of Experimental Example 7. The obtained metal member was twisted and warped after being heated to 150 ° C. and partially deformed.

(Example 8)

On the entire surface of a plate-like substrate (length: 200 mm) made of pure titanium (JIS type 1) with a thickness of 0.1 mm, a cut portion with a length of Omm is provided at an interval of 10 mm. Then, form a zigzag pattern in the same direction, and then apply a tensile force in a direction substantially perpendicular to the length direction of the cut portion to open the cut portion !! ~ 4mm to cause plastic deformation, and a permanent strained portion around the cut portion Formed. Next, this base material was charged in an electric furnace preheated to 400 ° C., heated in an air atmosphere for 30 minutes, and then taken out from the electric furnace to obtain a metal member of Experimental Example 8. The obtained metal member remained flat after being heated to 400 ° C. without being twisted or warped.

(Experimental example 9)

A corrugated plate with a pitch of 30 mm and a height of 15 mm was formed by bending a base material (length: 200 mm) made of pure titanium (JIS Class 1) to a thickness of 0.1 mm. Next, this base material was placed in an electric furnace preheated to 400 ° C., heated in the air atmosphere for 30 minutes, and then the electric furnace force was also taken out to obtain a metal member of Experimental Example 9. The obtained metal member was twisted and warped after being heated to 400 ° C. and partly deformed.

(Evaluation of heat resistance of metal parts)

In order to evaluate the heat deformation resistance of the metal member in Experimental Example 1, the force of heating at 1000 ° C or higher for 20 seconds until red hot using an acetylene gas wrench Shape that remains flat without twisting or warping Was kept. On the other hand, the metal member of Experimental Example 6 was similarly treated with acetylene. When it was heated with a gas spanner, it deformed significantly.

According to the above experimental examples;! To 4, 6 to 9, experimental examples in which a permanent strain part was formed at a narrow pitch; the base materials of! Therefore, even if heating spots occur in the subsequent heating operation, it is possible to prevent the base material from being deformed as in Experiments 6, 7, and 9, and to have a large area of catalytic activity without deformation such as twisting or warping. It became clear that it was possible to produce metal parts with

(Test Example 1)

In Test Example 1, the removal effect (deodorization effect) of the ammonia gas from the metal member was examined.

Yes

A container formed in an approximately rectangular parallelepiped shape with an acrylic plate (with a volume of 32.8 U, a beaker into which 150 mL of tap water has been poured, and the metal member of Experiment 1 (not heated with an acetylene gas spanner) beaker) Then, the container was folded and immersed so that it was completely immersed in the tap water, and then, after injecting 1 mL of 28% ammonia water into the container, the container was sealed, and the ammonia volatilized from the ammonia water injected into the container The detection voltage (mV) corresponding to the amount of gas decrease after 3 hours was measured with a gas sensor (manufactured by Figaro), which indicates that the ammonia gas concentration in the container decreases. In addition, the container was placed under a certain place.

Next, in order to determine whether the ammonia gas in the container was removed by a metal member immersed in the water in the beaker or dissolved in the water in the beaker, a beaker containing only tap water was removed. The detection voltage of the sensor when placed in a container was measured in the same manner. Since this measured value is the detection voltage corresponding to the amount of gas removed by dissolving in the tap water in the beaker, this measurement value was offset and the detection voltage (mV) due to the influence of the metal member was obtained. The temperature in the container at the time of measurement was 26 ° C.

Similarly, the detection voltage due to the influence of the metal member was examined for the metal members of Experimental Examples 2 to 7 (The metal member of Experimental Example 6 was not heated with an acetylene gas wrench). In addition, instead of the metal member of Experimental Example 1, a plate-like base material (formation of uneven parts and heat treatment were performed with pure titanium (JIS type 1), 17 cm long, 10 cm wide, 0.1 mm thick) The same applies to the case of immersing a non-contained product in tap water in a beaker. The detection voltage was examined (Comparative Example 1).

Further, when the metal member of Experimental Example 1 was put in a container without being immersed in water, the detection voltage due to the influence of the metal member was similarly examined (Comparative Example 2). In the case of Comparative Example 2, since the metal member is not immersed in water, the beaker into which water has been poured is not placed in the container.

Table 1 summarizes the detection voltage (detection voltage decreased over 3 hours) due to the influence of the metal members of the experimental examples;! To 7 and Comparative Examples 1 and 2.

[table 1]

In Table 1, when comparing the decrease values of the detection voltages of Experimental Examples 1 to 5, in the case of Experimental Example 4 in which the substrate was heated to 500 ° C after the formation of the concavo-convex part, the detection voltage hardly decreased. On the other hand, in Experimental Example 5 in which the concavo-convex part was formed without heating the base material, in the experimental example in which the base material was heated to 200 to 450 ° C. with the concavo-convex part;! To 3, the detection voltage was about 0. lmV has also decreased. In addition, when the decrease value of the detection voltage in Experimental Examples 6 and 7 and Comparative Example 1 are compared, in Experimental Example 6 in which the base material was heated to 300 ° C, the detection voltage decreased by approximately 0.1 mV, whereas 150 ° C It can be seen that the detected voltage did not decrease in Example 7 heated to C and Comparative Example 1 that was not heated.In addition, the detected voltage did not decrease in Comparative Example 2 where the metal member was not immersed in water. Was confirmed.

From the above, the metal member with the uneven part formed on the base material by plastic deformation and the metal member heated at a temperature of 200 to 450 ° C are malodorous substances even under certain conditions as in this test example. It was confirmed that ammonia can be decomposed. The effect is that the metal member is immersed in water. It was confirmed that it became noticeable by soaking.

(Test Example 2)

In Test Example 2, dimethyl sulfide, which is sparingly soluble in water, was used to examine the effect of decomposing its odor by metal members.

A container formed in an approximately rectangular parallelepiped shape with an acrylic plate (with a capacity of 32.8 U, place a beaker into which 150 mL of tap water has been poured, and immerse the metal member of Experimental Example 2 so that it is completely immersed in the tap water in the beaker. Next, after 0.5 mL of dimethyl sulfide was injected into the container, the container was sealed, and a detection voltage (mV) corresponding to the amount of decrease in gas volatilized from the dimethyl sulfide injected into the container after 3 hours was applied. Measured with a gas sensor (manufactured by Figaro) A decrease in the detection voltage indicates that the concentration of dimethyl sulfide gas in the container decreases, and the container was placed under a certain place.

Next, in order to determine whether the dimethyl sulfide gas in the container was removed by the metal member immersed in the water in the beaker or dissolved in the water in the beaker, a beaker containing only tap water was placed in the container. The detection voltage of the sensor when placed in was measured in the same manner. Since this measurement value is the detection voltage corresponding to the amount of gas removed by dissolving in the tap water in the beaker, this measurement value was offset and the detection voltage (mV) due to the influence of the metal member was obtained. The temperature in the container at the time of measurement was 26 ° C.

As a result, the detection voltage due to the influence of the metal member in Experimental Example 2 (detection voltage decreased during 3 hours) was 0.2 mV.

Based on the above, metal members with irregularities formed on the base material by plastic deformation and metal members heated at a temperature of 200 to 450 ° C can be used even in a room with a small amount of ultraviolet irradiation as in this test example. It was confirmed that dimethyl sulfide, which is a poorly soluble malodorous substance, can also be decomposed. The phenomenon that malodorous substances can be decomposed in a place that is not irradiated with ultraviolet rays has not been confirmed in crystalline anatase-type titanium oxide, so the oxide layer of the metal members in Experimental Examples 1 to 3, 5, and 6 Is a narrow forbidden energy that is different from the forbidden energy zone of amorphous titanium oxide and crystalline titanium oxide because of the presence of an interface between amorphous titanium oxide and crystalline titanium oxide. It is presumed that a band was formed at the interface. The energy gap at the interface is smaller than the thermal energy at room temperature, so ultraviolet Even if no line is irradiated, it is assumed that electrons are excited from the valence band to the conduction band at room temperature to exhibit catalytic activity! /.

(Test Example 3)

Next, the physical properties of water when the metal member of the present invention was immersed in water were measured using FTIR (Fourier Transform Infrared Spectrometer: Model FTIR-8100M, manufactured by Shimadzu Corporation) and NMR (Nuclear Magnetic Resonator: JEOL). The measurement was made using a model AL-400). In FTIR, the ATR method was used. In addition, the measurement conditions for NMR ¹ H-nuclear magnetic resonance spectrum (400 MHz, reference magnetic field 9.39T, measurement nuclide 1H, 13C) are as follows: measurement temperature 22.9 ° C, pulse width; 5.4 ^ 8, Total number of times: 32 times. The chemical shift was expressed in relative position using a heavy-chloroform solution with a small amount of tetramethylsilane added as a reference substance and the tetramethylsilane proton signal as the reference peak (Oppm).

For water measured by FTIR and NMR, a metal part (length 30 cm, width 40 cm, thickness 0.1 mm) prepared in the same manner as in Example 2 was immersed in 1 liter of tap water and stored at room temperature. After leaving for 10 days, the metal member was taken out. For comparison, we also measured 1L of tap water left at room temperature for 10 days.

Fig. 5 is a spectrum showing the wave number and absorbance of FTIR (ATR method), and Fig. 6 is a spectrum showing the ratio of wave number and absorbance of FTIR (ATR method).

The absorption peak of water is the force observed in the vicinity of ΟδδΟοπ ¹ and ZZOOcnT ^{1. As} is clear from FIGS. 5 and 6, the example in which the metal member of the present invention was immersed in water and the blank (the metal member was not immersed) Then, there is a clear difference in peak wavenumber and absorbance. From this result, it is shown that the metal member of the present invention causes some change in the vibration and rotation of water molecules.

Further, according to the analysis result by NMR, the chemical shift of the water in which the metal member of the present invention is immersed is 4.797 ppm (4.81 ppm in the case of water in which the metal member is not immersed), and the water in which the metal member of the present invention is immersed is The full width at half maximum was 0.004571 ppm (0.05625 ppm in water without immersing metal parts), and it was confirmed that both the chemical shift and the full width at half maximum decreased. From this result, it is shown that the metal member of the present invention reduces the aggregate (defined as a cluster) of water molecules. From the above analysis results, it is surmised that the metal member of the present invention makes the contacted water molecule cluster smaller and causes some change in the vibration and rotation of the water molecule. Although the mechanism by which malodorous substances in the gas in contact with the water in which the metal member of the present invention is immersed is not clearly understood, the cluster of water molecules is reduced by the metal member of the present invention. It is inferred that there is a relationship.

[0064] (Test Example 4)

Tests so far have shown that the metal member of the present invention exhibits a decomposition effect (catalytic effect) of malodorous substances in indoor rooms where the amount of ultraviolet irradiation is small, but the catalytic effect is exhibited when the amount of ultraviolet irradiation is large. It was evaluated by a methylene blue fading test. The fading test is performed by immersing the metallic member of Experimental Example 2 in a shallow glass container containing a constant concentration of methylene blue aqueous solution, and continuously irradiating the liquid surface of the methylene blue aqueous solution with ultraviolet light at each elapsed time. This was done by measuring the light transmittance of the aqueous methylene blue solution. For comparison, the metal member was immersed, and the liquid surface was irradiated with an ultraviolet ray in the same manner.

The UV irradiation equipment used was a UV tube manufactured by Toshiba Lighting & Technology (GLS-6T, wavelengths 253 nm, 185 nm), and the UV irradiation amount was on the liquid surface of the methylene blue aqueous solution. . The light transmittance was measured by injecting a methylene blue aqueous solution collected from the container every elapsed time into a cell attached to a photocatalytic effect measuring device (PE-01 manufactured by Koper Electronics). This fading test shows that the higher the light transmittance, the more methylene blue is decomposed.

Table 2 shows the light transmittance of the methylene blue aqueous solution immersed in the metal member of Experimental Example 2 and the light transmittance of the methylene blue aqueous solution immersed in the metal part (blank) for each elapsed time. It is. The light transmission in Table 2 was normalized using the formula (light transmission at initial (0 minutes)) ÷ (light transmission at each passing time).

[0065] [Table 2]

[0066] From the results in Table 2, it was confirmed that by irradiating the metal member of Experimental Example 2 with ultraviolet rays of high-engineering energy having a short wavelength of 253 nm and 185 nm, methylene blue was decomposed and the aqueous solution could be faded. It was. This indicates that the metal member of Experimental Example 2 exhibited a photocatalytic effect. Since it is known that the photocatalytic effect is caused by crystalline anatase-type titanium oxide, from the results of this test example, the oxide layer of the metal member of Experimental Example 2 is an amorphous material formed by thermal oxidation. It was confirmed that it contains titanium oxide and crystalline titanium oxide.

When the same test was performed using the metal members of Experimental Examples 1, 3, 5, 6, and 8, all exhibited a photocatalytic effect. This confirms that the oxide layers of the metal members of Experimental Examples 1, 3, 5, 6, and 8 also contain amorphous titanium oxide and crystalline titanium oxide formed by thermal oxidation. It was.

[0067] (Test Example 5)

Next, using the metal member of Experimental Example 6, the effect of preventing the deterioration of edible oil was confirmed. Asked the lunch box shop for business to cooperate, salad oil tank (10U of the metal parts of Experiment 6 was immersed in 18U, and the acid value of salad oil when the same number of deep-fried foods were fried) The acid value was determined by titration with an ethanol solution of potassium hydroxide using phenolphthalein as an indicator.For comparison, normal operations in which fried foods were carried out without immersing metal parts were performed. The acid value of the oil at the time was also measured.

As a result, the oil obtained by frying the fried food without immersing the metal member exceeded the acidity strength on the 8th day. In general, lunch boxes and the like replace the oil with a new one when the acidity strength exceeds ¾. However, in the case of oil fried by immersing a metal member, the acidity strength after ¾ It was as follows. As described above, it has been clarified that the deterioration of the salad oil can be prevented by using the metal member of this experimental example. It is expected that fossil fuel processed products such as lubricants and insulating oils can be prevented from deterioration as well.

[0068] (Test Example 6)

A metal member of Experimental Example 2 cut to a width of 20 mm (150 mm in length) was placed in a gasoline tank of an automobile and immersed in gasoline, and a fuel consumption test was performed to measure gasoline consumption during driving. The vehicle used for the measurement was Suzukiart (first year registration: November 27, 2000, model GF-HA12S, prime mover model F6A). For comparison, the fuel economy was also measured when metal parts were not placed in the gasoline tank.

With the fuel full, there was almost no inclination and no traffic lights. The vehicle traveled 10 km on a general road 11 km (total mileage 220 km), and the fuel consumption after driving was measured.

As a result, the fuel consumption when the metal parts were not immersed in the gasoline tank was 22.4L (average value of two experiments), whereas the fuel consumption when the metal parts were immersed in the gasoline tank was 18. 7L (average of 10 experiments).

As described above, according to the present example, it has become clear that the fuel consumption can be reduced by about 20%. In addition, fuel efficiency improvement effects can be expected for various fuels such as heavy oil, light oil, and kerosene that can be obtained using only gasoline.

Thus, it was confirmed that the metal member of this example has catalytic activity even in a place such as a gasoline tank.

[0069] (Test Example 7)

Two containers with 0.6L of tap water were prepared in one container, 50 metal members from Experiment 2 were placed in only one container, and the two containers were left in an indoor place for 7 days. When the redox potential of tap water in the container was measured with an oxidation-reduction potentiometer (ORP-203), the initial redox potential of tap water was 726 mV. The redox potential of tap water immersed in a metal member was 7 days later, it was 434 mV (about 60% of the initial value). On the other hand, the oxidation-reduction potential after 7 days of tap water without immersing the metal members was 698 mV (about 96% of the initial value). As described above, according to the present example, it was confirmed that the metal member on which the oxide layer was formed had a reducing power for reducing tap water at a certain place. [0070] (Test Example 8)

Prepare two glass petri dishes with standard agar medium for general bacterial tests and two glass petri dishes with desoxycholate medium for coliform bacteria test. One standard agar medium and desoxycholate To the medium, the powder lg of the oxide layer prepared by shaving the surface (oxide layer) of the metal member of Experimental Example 2 was added. Each glass petri dish was filled with 10 mL of contaminated urban river water. In the general bacterial test, the number of bacteria was counted after 24 hours of incubation at 36 ° C. In the coliform group test, the number of bacteria was counted after culturing at 36 ° C for 20 hours in a certain place. The test was conducted at the Saitama Environmental Research Association. Table 3 shows the bacterial count results.

[0071] [Table 3]

[0072] From Table 3, it can be seen that in the medium to which the oxidized layer powder was added (indicated as “added” in the table), the general bacteria were compared to the medium to which the oxidized layer powder was not added (indicated in the table as “blank”). It was found that the number of coliforms decreased to about 30%, and the coliform group decreased to about 70%.

As described above, according to the present example, it was confirmed that the oxide layer of the metal member has an action of suppressing the growth of general bacteria and coliform bacteria even in some places.

[0073] (Test Example 9)

The metal member of Example 5 was cut in half in the width direction to a length of 17 cm and a width of 5 cm. This metal member was rolled up into a cylindrical shape, and prepared in 300 mL of light oil for 1 hour, for 3 hours, for 5 hours, or not immersed at all.

Each diesel oil was used as fuel and a diesel engine generator with a resistance (33 Ω) connected to the output side was driven to measure the output voltage and the concentration of carbon monoxide in the exhaust gas. Measurements were taken for 5 minutes, 10 minutes, and 18 minutes every minute after driving the generator for each fuel, and the average of the 10 points was obtained. The resistor is connected to the output side of the generator to stabilize the generator speed, and the output voltage is the voltage at both ends of this resistor. The pressure was measured.

As a result, the output voltage tended to increase as the immersion time of the metal member increased, compared to 92.4 V for the fuel without the metal member immersed, and 93.6 V with the fuel immersed for 5 hours. It was. In addition, the carbon monoxide concentration in the exhaust gas was 0.040% for the fuel that did not immerse the metal member, but it tended to decrease as the immersion time for the metal member increased. It was 0.031%.

As described above, according to this example, as the immersion time of the metal member in the fuel increases, the output voltage of the generator increases and the carbon monoxide concentration in the exhaust gas decreases. It was confirmed that the fuel can be reformed by the metal member.

[0074] (Test Example 10)

A base material made of pure titanium (JIS class 1) and having a diameter of 0.5 mm was placed in an electric furnace preheated to 300 ° C and heated in air for 30 minutes. The metal member of Experimental Example 10 in which an oxide layer was formed on the surface of the base material was obtained by taking out and cooling.

12 g of the metal member of Experimental Example 10 was immersed in 200 mL of tap water in which the faucet power was also poured into a cup and left at room temperature. After 10 minutes of tasting, the chlorine odor disappeared and the taste changed to mineral water. Note that the odor of chlorine was not lost in tap water left for 10 minutes by pouring into a glass from the faucet. The change in the force S and the taste of water explained in Test Example 3 that the change that can be detected by FTIR and NMR occurs in the water by immersing the metal member of the present invention in water. I guess there is a relationship.

[0075] (Test Example 11)

In a bottle containing 50 mL each of sake, shochu, whiskey, and wine, 3 g of the metal member of Experimental Example 10 was immersed and allowed to stand at room temperature. When tasting 6 hours after immersing the metal parts, all the alcoholic beverages had a mild taste. When FTIR and NMR were measured for sake, shochu, and whiskey before and after immersion of metal parts, there was a difference in the absorption level in the vicinity of the absorption wave number S OOcnT ^{1 in} FTIR, and a difference in the half-value width in NMR. . I guess that changes in the taste of liquors have something to do with these things [0076] Further, when water in which the metal member of this example was immersed was poured into a sprayer and sprayed on clothes to which tobacco odor was attached, the tobacco odor of the clothes was reduced, and the light odor disappeared. In addition, when the metal member of this example was placed in a vase containing cut flowers, the water in the vase did not rot until the flowers withered. Furthermore, when sprouts were grown in water immersed in the metal member of this example, germination and growth could be promoted.

As described above, according to the present example, it was confirmed that the metal member can be modified by immersing it in a liquid such as water or liquor to change the taste of the liquid.

Industrial applicability

[0077] The present invention relates to a metal member having catalytic activity that is effectively used for water or air purification, sterilization, deodorization, antifouling, food freshness maintenance, oil deterioration prevention, reduction in the amount of petroleum fuel used, and the like. With regard to its manufacturing method and its usage, its catalytic action is exerted even in places such as indoors and shoeboxes where the amount of ultraviolet irradiation is low, and water and air purification, sterilization, deodorization, antifouling, food freshness preservation and Prevents oil degradation, reduces the amount of petroleum fuel used, etc., and shows superior stability over time with no decrease in catalytic activity due to falling off of the oxide layer, and contamination with metal powder, dust, etc. Can be used in factories and equipment such as semiconductors, foods, automobiles, boilers, oil stoves, and other combustion equipment, and can be used for metal parts with excellent applicability. Even indoors, in shoe boxes or in fuel tanks Water and air purification, sterilization, deodorization, antifouling, food freshness preservation, oil deterioration prevention, and reduction in the amount of petroleum fuel used. Antibacterial properties, decomposition effects of organic substances and offensive odors and malodorous substances, preservation of freshness of foods, prevention of oil deterioration, and reduction of oil fuel consumption in certain places such as indoors and shoeboxes where UV irradiation is low The usage method of the metal member which can be exhibited can be provided.

Claims

The scope of the claims

[1] A metal base material, and an oxide layer containing a catalytically active amorphous oxide and a crystalline oxide formed on the surface of the base material by thermal oxidation. A metal member characterized by

[2] It is characterized by comprising a metal base material having a plurality of permanent strained portions formed in response to an external force, and an oxide layer having catalytic activity in which the surface of the permanent strained portion is oxidized. Metal member to be used.

[3] The metal member according to [1], wherein the material of the base material is titanium or a titanium alloy.

[4] The metal member according to [2], wherein the base material is made of titanium or a titanium alloy.

[5] The surface of the base material is heated by heating the metal base material to a temperature of 200 to 450 ° C. under normal pressure and / or forming permanent strain portions at a plurality of locations on the surface of the metal base material. A method for producing a metal member, characterized by comprising an oxide layer forming step of oxidizing the metal to form an oxide layer having catalytic activity.

[6] The base material is formed in a plate shape, a foil shape, or a tape shape, and the permanent strained portion is forged with a hammer or between two dies having irregularities formed on the surface so as to mate with each other. 6. The method for producing a metal member according to claim 5, wherein the metal member is a processed uneven portion.

[7] In any of the forces 1 to 4, the metal member according to 1 or the metal member produced by the method of claim 5 or 6 is immersed in the liquid, and the liquid is irradiated with ultraviolet rays. A method of using a metal member characterized by being brought into contact with a gas under weak excitation light of less than 01 W / m ² or in a remote place.