Alloy member, joined body, device, method for manufacturing alloy member, and method for manufacturing joined body

Abstract

To provide an alloy member which is excellent in adhesion to a resin film.SOLUTION: An alloy member 200 includes a base material 101 containing magnesium and lithium, and a corrosion prevention film 102 which is provided on the base material 101, and contains magnesium, phosphorus and fluorine. The corrosion prevention film 102 has at least one first recess 111 on a surface opposite to the base material 101, and the surface of the first recess has at least one second recess 112 smaller than the first recess.SELECTED DRAWING: Figure 8

Description

[Technical Field]

[0001] The present disclosure relates to an alloy member, a joined body, an apparatus, a method for manufacturing an alloy member, and a method for manufacturing a joined body containing magnesium and lithium. [Background technology]

[0002] Magnesium-lithium alloys, which contain magnesium and lithium, are used in a variety of products due to their light weight and excellent mechanical strength. In addition, for products that require lightweight construction, it is known to avoid fastening with screws and instead join two components using a bonding resin made from a hardened adhesive.

[0003] However, it is known that when an alloy member made of an alloy containing magnesium is joined to another member with a joining resin, a brittle layer is formed at the interface between the alloy member and the joining resin, making it difficult to obtain the desired adhesive strength.Patent Document 1 discloses a technology for improving adhesive strength by providing a porous magnesium oxide layer on the surface of an alloy whose main component is magnesium using a micro-arc oxidation process, which is a type of anodizing process. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-308757 Summary of the Invention [Problem to be solved by the invention]

[0005] In the method disclosed in Patent Document 1, the pore size of the porous layer cannot be made large enough, which sometimes results in insufficient adhesion of the bonding resin (cured adhesive).In addition, even if a resin coating film is formed on the alloy by curing a resin material, it sometimes peels off. [Means for solving the problem]

[0006] A first aspect for solving the above problem is an alloy component comprising a substrate containing magnesium and lithium and a corrosion-resistant film containing magnesium, phosphorus, and fluorine provided on the substrate, wherein the corrosion-resistant film has at least one first recess on a surface opposite the substrate, and the surface of the first recess has at least one second recess smaller than the first recess.

[0007] A second aspect for solving the above problem is a joined body comprising the above alloy member, a joined member, and a joining resin that joins the alloy member and the joined member, characterized in that a portion of the joining resin is provided in the first recess and the second recess.

[0008] A third aspect for solving the above-mentioned problems is a method for manufacturing an alloy member, comprising the steps of: placing an anode and a cathode in an electrolytic solution; and applying a voltage between the anode and the cathode to form an anticorrosion film on the anode; wherein the anode contains magnesium and lithium; the electrolytic solution contains fluorine, ammonium, and phosphorus; and the proportion of fluorine ions in the electrolytic solution relative to the total amount of phosphate ions and fluorine ions is in the range of 88% or more and 99.5% or less.

[0009] A fourth aspect for solving the above problem is a method for manufacturing a joined body in which an alloy member and a workpiece are joined via an adhesive, the method comprising the steps of: preparing an alloy member using the above-described method for manufacturing an alloy member; placing an adhesive on the alloy member and / or the workpiece; and hardening the adhesive to form a joining resin that joins the alloy member and the workpiece. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide an alloy member having excellent adhesion to a resin film, and a joined body having excellent adhesion between the alloy member and a joining resin. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic view of a bonded body according to a first embodiment. [Figure 2] (a) is a 50x SEM image of the surface of the anticorrosion film according to the first embodiment, and (b) is a 500x SEM image of the surface of the anticorrosion film according to the first embodiment. [Figure 3] FIG. 3 is a schematic diagram illustrating a first normal and a second normal according to the first embodiment. [Figure 4] FIG. 2 is a flow chart showing a manufacturing process of the bonded body according to the first embodiment. [Figure 5] 1 is a schematic view of an anodizing apparatus for manufacturing alloy members of a joined body according to the first embodiment. [Figure 6] 1A is a schematic diagram of a radiation imaging apparatus that is a modified example of the first embodiment, and FIG. 1B is a schematic diagram of a radiation imaging apparatus that is a modified example of the first embodiment. [Figure 7] 7 is a schematic diagram of the radiation imaging apparatus shown in FIG. 6(b) at cross section II. [Figure 8] FIG. 4 is a schematic view of an alloy member according to a second embodiment. [Figure 9] FIG. 10 is a schematic diagram of an optical device / photographing device that is a modified example of the second embodiment. [Figure 10] FIG. 2 is a schematic diagram showing a method for evaluating adhesive strength in Examples and Comparative Examples. [Figure 11] FIG. 10 is a graph showing the relationship between the proportion of first recesses and the content of fluorine ions relative to the total of phosphate ions and fluorine ions in the electrolyte solution. [Figure 12] 10 is an SEM-EDS image of the anticorrosion coating of Example 2, taken from the surface near the center in the thickness direction. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings.

[0013] First Embodiment FIG. 1 is a schematic diagram of a bonded structure according to the first embodiment, showing a cross section cut in the stacking direction. The bonded structure 100 includes a substrate 101, an anticorrosion film 102 provided on the substrate 101, a bonding resin 103, which is a cured product of an adhesive provided on the anticorrosion film 102, and a bonded member 104. In the first embodiment, the substrate 101 provided with the anticorrosion film 102 is referred to as an alloy member 105. The use of the bonded structure according to this embodiment is not particularly limited, and it can be used as a structure according to the user's application, such as an exterior member (housing), an interior member, or a sliding member for a device having components.

[0014] (base material) The substrate 101 is made of an alloy containing magnesium and lithium, and is preferably made of a magnesium-lithium alloy (hereinafter referred to as Mg-Li alloy) containing magnesium as the main component and lithium. In this specification, the term "main component" refers to the element that has the largest total mass among the elements contained in a substrate made of multiple elements, or the compound that has the largest total mass among the compounds contained in a substrate made of multiple compounds.

[0015] Among Mg-Li alloys, those for use as the substrate 101 preferably have a sum of magnesium (Mg) and lithium (Li) contents of 90% by mass or more. When the sum of the magnesium content and lithium content is 90% by mass or more, the alloy becomes lighter than magnesium alloys that do not contain lithium. Furthermore, Mg-Li alloys have superior vibration-damping properties and specific strength compared to magnesium alloys that do not contain lithium. Superior vibration-damping properties mean that vibrations are quickly converged by quickly converting vibration energy into thermal energy. Furthermore, specific strength is the tensile strength per density, and the higher the specific strength, the lighter the component can be.

[0016] In addition to magnesium and lithium, the Mg-Li alloy may contain aluminum (Al) and zinc (Zn), and may further contain germanium (Ge) and / or beryllium (Be). In addition to the elements mentioned above, the alloy may contain at least one element selected from the group consisting of zirconium (Zr), calcium (Ca), silicon (Si), and manganese (Mn), with the remainder consisting of inevitable impurities and magnesium. Examples of inevitable impurities include iron (Fe), copper (Cu), cobalt (Co), and nickel (Ni).

[0017] The lithium (Li) content in the Mg-Li alloy is preferably in the range of 0.5% by mass to 15% by mass. If it is less than 0.5% by mass, it will not be possible to make the alloy lighter than the magnesium alloy, and if it is more than 15% by mass, the vibration damping properties may be insufficient. Preferably, it is in the range of 5% by mass to 11% by mass, in which the α phase and the β phase coexist. In this range, the corrosion resistance and mechanical strength of the substrate 101 are high, making it suitable as a structural material.

[0018] The aluminum (Al) content in the Mg-Li alloy is preferably in the range of 1% by mass to 8% by mass. Al plays a role in increasing the fracture strength of the substrate 101, and when the Al content is in the above range, the mechanical strength can be made sufficient compared to when no Al is contained. It is believed that this is because Al reacts with Mg and / or Li, and these compounds, such as Al-Li compounds, Mg-Al compounds, and Mg-Li-Al compounds, precipitate, thereby increasing the mechanical strength. A more preferred content is in the range of 3% by mass to 7% by mass.

[0019] The total content of germanium (Ge) and beryllium (Be) in the Mg-Li alloy is in the range of 0.02% by mass to 0.4% by mass. Ge and Be partially replace Al, thereby enhancing the corrosion resistance of the substrate 101. As described above, Mg-Li alloys containing Al have increased mechanical strength due to the reaction of Al with Mg and / or Li. However, this reaction results in the segregation of lithium-rich grain boundaries in the matrix, making the alloy more susceptible to corrosion. However, by partially replacing Al with elements such as Ge and Be, which have smaller atomic radii than Al, Ge and Be are actively placed at the grain boundaries in place of Li, thereby suppressing the segregation of Li to the grain boundaries. This improves corrosion resistance. The content of Ge alone is preferably in the range of 0.01% by mass to 0.4% by mass. More preferably, it is in the range of 0.01% by mass to 0.2% by mass. Furthermore, the content of Be alone is preferably in the range of 0.02% by mass to 0.1% by mass. It is more preferable that the content is in the range of 0.01% by mass or more and 0.05% by mass or less.

[0020] The zirconium (Zr) content in the Mg—Li alloy is preferably in the range of 0.6 mass % to 3.0 mass % because this prevents the grain size from becoming coarse during the solidification process from the liquid phase to the solid phase during the production of the base material 101.

[0021] Zinc (Zn), calcium (Ca), silicon (Si), and manganese (Mn) in the Mg-Li alloy play a role in increasing the strength of the substrate 101. The sum of the contents of these elements is preferably in the range of 0.01% by mass to 5% by mass. Zn is preferably contained at 3% by mass or less, more preferably in the range of 0.1% by mass to 2% by mass. Ca is preferably contained at 3% by mass or less, more preferably in the range of 0.1% by mass to 1.0% by mass. Si is preferably contained at 0.2% by mass or less, more preferably in the range of 0.1% by mass to 0.2% by mass. Mn is preferably contained at 0.5% by mass or less, more preferably in the range of 0.1% by mass to 0.2% by mass.

[0022] The substrate 101 may contain metal elements other than those exemplified above, provided that the properties are not affected. These metal elements also include unavoidable impurities that are unavoidable during manufacturing. Examples of unavoidable impurities include Fe, Cu, Co, and Ni. The content of each element is 0.1% by mass or less, and the total content of unavoidable impurities is 1% by mass or less.

[0023] The raw material of the Mg-Li alloy is not particularly limited, and examples of commercially available alloys include LZ91, LAZ771, LAZ941, and Ares manufactured by Anlih Materials Technology Co., Ltd.

[0024] The thickness of the substrate 101 is not particularly limited, but from the viewpoint of ensuring sufficient rigidity, it is preferably thicker than the thickness of the anticorrosion film 102 .

[0025] (Anti-corrosion film) The anticorrosion coating 102 is provided on the substrate 101. The anticorrosion coating 102 contains magnesium (Mg), phosphorus (P), fluorine (F), and oxygen (O). Preferably, the anticorrosion coating 102 further contains lithium (Li). The average thickness of the anticorrosion coating 102 is preferably 20 μm or more, and more preferably greater than 20 μm. This is because it is possible to prevent water from diffusing into the assembly 100 and reaching the interface between the anticorrosion coating 102 and the substrate 101 for a long period of time. Therefore, even if water seeps in from the surface of the anticorrosion coating 102, it is possible to reduce the possibility of the water reaching the substrate 101.

[0026] The anticorrosion coating 102 has two surfaces. One is surface 102B that contacts the substrate 101, and the other is surface 102A that contacts the bonding resin 103. In other words, surface 102A is the surface provided on the opposite side from the substrate 101. The anticorrosion coating 102 is a porous body having a plurality of pores 106.

[0027] 2A and 2B are SEM (Scanning Electron Microscope) images of the surface 102A of the anticorrosion coating 102. Fig. 2A is an image at a magnification of 50 times, and Fig. 2B is an image at a magnification of 500 times.

[0028] The surface 102A of the anticorrosion coating 102 has at least one first recess 111. The surface 111A of the first recess 111 has at least one second recess 112 that is smaller than the first recess 111. The second recess 112 may be a through hole. By providing a portion of the bonding resin 103 in the first recess 111 and the second recess 112, the adhesion between the anticorrosion coating 102 and the bonding resin 103 is increased, resulting in sufficient bonding strength between the alloy member 105 and the bonded member 104. This is because, when bonding the alloy member 105 and the bonded member 104, an adhesive, which is a precursor of the bonding resin 103, is provided on the anticorrosion coating 102, and the adhesive penetrates into the first recess 111 and the second recess 112 and hardens. That is, the bonding resin 103 contacts the region 102AA of the surface 102A other than the recess, the surface 111A of the first recess, and the surface 112A of the second recess. Since the bonded body 100 has the second recess 112, the contact area between the anticorrosion coating 102 and the bonding resin 103 is larger than in a bonded body not having the second recess 112. Therefore, the adhesion between the anticorrosion coating 102 and the bonding resin 103 is stronger than in a bonded body not having the second recess 112.

[0029] From the viewpoint of increasing the adhesive strength between the anticorrosion coating 102 and the bonding resin 103, it is preferable that the first recess 111 and the second recess 112 are formed facing in different directions. That is, it is preferable that the direction of the first normal 111N, which is a line perpendicular to the imaginary plane filling the first recess, intersects the direction of the second normal 112N, which is a line perpendicular to the imaginary plane filling the second recess. When the directions of the two normals satisfy the above relationship, even if an external force acts in the direction (direction of the normal 111N) in which the bonding resin 103 tries to come out of the first recess 111, the direction is different from the direction (direction of the normal 112N) in which the second recess 112 is likely to come out, and therefore the protruding portion of the bonding resin 103 that has entered the second recess 112 is unlikely to come out. This enhances the so-called anchor effect.

[0030] The average equivalent circular diameter R1 of the first recesses 111 is preferably 30 μm or more, and more preferably greater than 30 μm. The average equivalent circular diameter R1 can be measured, for example, using an SEM image. This image is a planar image of the region 102AA of the surface 102A other than the recesses. In other words, the average equivalent circular diameter R1 of the first recesses 111 is the size of the first recesses 111 that can be measured when viewed in planar view of the region 102AA of the surface 102A.

[0031] To make the average equivalent circle diameter R1 of the first recesses 111 larger than 30 μm, the content ratio of fluorine ions must be set to a predetermined condition in the anodizing treatment described later. This condition will be explained in the manufacturing method section.

[0032] The distance D between adjacent first recesses 111 on the surface 102A is preferably larger than the average circular equivalent diameter R1 of the first recesses 111. This is because a sufficiently large area of ​​the region 102AA can easily increase the joining strength between the alloy member 105 and the member to be joined 104. In addition, it can easily ensure that the strength of the anticorrosion coating 102 itself is sufficient.

[0033] The distribution density of the first recesses 111 on the surface 102A is 5 pieces / mm 2 More than 50 pieces / mm 2 The range is preferably 10 pieces / mm or less, and more preferably 10 pieces / mm 2 That's all. If the proportion of first recesses 111 is too large, the strength of anticorrosion coating 102 itself will be insufficient, and it may break even with a small force, resulting in insufficient bonding strength. On the other hand, if the proportion is too small, the contact area with bonding resin 103 will be small, and the aforementioned anchor effect may not be fully realized.

[0034] The average equivalent circular diameter R2 of the second recesses 112 is preferably 10 μm or less, and more preferably less than 10 μm. The average equivalent circular diameter R2 can be measured, for example, using an SEM image. This image is a planar image of the region 102AA of the surface 102A other than the recesses. In other words, the average equivalent circular diameter R2 of the second recesses 112 is the size of the second recesses 112 that can be measured when viewed in plan with respect to the region 102AA of the surface 102A.

[0035] The number of second recesses 112 on the surface 111A of the first recess is preferably in the range of 5 to 100. This is because increasing the number of protrusions of the bonding resin 103 that enter the second recesses 112 increases the bonding strength between the alloy member 105 and the bonded member 104.

[0036] The fluorine content in the surface 111A of the first recess and the surface 112A of the second recess is preferably higher than the fluorine content in the region 102AA of the anticorrosion coating surface 102A other than the recess. When the fluorine content in the surface 111A of the first recess and the surface 112A of the second recess is higher than the fluorine content in the region 102AA, the uncured adhesive is more likely to be absorbed into the surface 111A and the surface 112A than into the region 102AA. Therefore, more adhesive penetrates into the first recess and the second recess than when the fluorine content in the surface 111A of the first recess and the surface 112A of the second recess is equal to or lower than the fluorine content in the region 102AA. As a result, the bonding strength between the alloy member 105 and the bonded member 104 is increased.

[0037] It is assumed that phosphorus exists as a magnesium phosphate compound in the anticorrosion coating 102. If magnesium phosphate is present in large amounts near the interface (surface 102B side) between the substrate 101 and the anticorrosion coating 102 for the lithium-containing substrate 101, oxygen contained in the magnesium phosphate may react with lithium contained in the substrate to form lithium oxide (LiO). This lithium oxide reacts with water and may deteriorate the durability of the assembly in a high-temperature, high-humidity environment. Therefore, it is preferable that magnesium phosphate is present in large amounts on the surface 102A side of the anticorrosion coating 102.

[0038] The fluorine concentration in the region of the anticorrosion coating 102 closer to the substrate 101 (the surface 102B side) is preferably higher than the fluorine concentration in the region of the coating 102 farther from the substrate 101 (the surface 102A side). This means that the content of inorganic fluoride in the region of the anticorrosion coating 102 near the substrate 101 is high, and the content of inorganic oxide is low. If inorganic oxide is present in a large amount in the region including the vicinity of the interface between the substrate 101 and the coating 102, oxygen and lithium may react to form lithium oxide. The type of inorganic fluoride is not particularly limited, but magnesium fluoride (MgF2), in which magnesium and fluorine can exist stably, is preferably present as the main component. If magnesium fluoride is present in a large amount in the region including the vicinity of the interface between the substrate 101 and the anticorrosion coating 102, fluorine in magnesium fluoride may react with lithium to form lithium fluoride (LiF), but lithium fluoride is stable in water. Therefore, durability is unlikely to be impaired. Therefore, it is preferable that the concentration of magnesium fluoride is high in the vicinity of the substrate 101 of the anticorrosion coating 102 .

[0039] (bonding resin) The bonding resin 103 is a hardened adhesive, and serves to bond the alloy member 105 and the member to be bonded 104 together.

[0040] The material of the bonding resin 103 is not particularly limited, but for example, a solventless adhesive using a urethane resin or an epoxy resin can be used. The viscosity of the adhesive, which is the precursor of the bonding resin 103, is in the range of 5 Pa·s to 100 Pa·s. Even with such a high viscosity adhesive, it is possible to achieve the anchoring effect described above as long as the first recess is larger than 30 μm.

[0041] The elastic modulus of the bonding resin 103 is preferably in the range of 0.1 GPa to 15 GPa. If the elastic modulus is in this range, the bonded body 100 can absorb the impact even if it is dropped, and separation between the alloy member 105 and the bonded member 104 is unlikely to occur. A more preferable range is 0.2 GPa to 5 GPa.

[0042] The thickness of the bonding resin 103 is preferably in the range of 3 μm to 150 μm, which absorbs the impact even if the bonded body 100 is dropped, and prevents peeling between the alloy member 105 and the bonded member 104. A more preferable thickness is in the range of 5 μm to 50 μm.

[0043] (Parts to be joined) The member to be joined 104 is a member to be joined to the alloy member 105 via the joining resin 103. The material of the member to be joined 104 is preferably a lightweight material, such as carbon fiber reinforced plastic (CFRP), carbon, polyvinyl chloride, acrylic, polyester, or polymethyl methacrylate resin (PMMA). Alternatively, a metal material such as an Mg-Li alloy, an Mg alloy, or an Al alloy can be used.

[0044] As described above, the bonded structure of the present disclosure has a second recess smaller than the first recess on the surface of the anticorrosion coating, and a portion of the bonding resin is provided in the first recess and the second recess. Therefore, the present disclosure can provide a bonded structure with better adhesion between the anticorrosion coating and the bonding resin than conventional structures.

[0045] <Manufacturing method of the first embodiment> Next, a method for manufacturing a bonded body according to the present disclosure will be described with reference to Figures 4 and 5. Figure 4 is a flow diagram showing the manufacturing process of a bonded body. Figure 5 is a schematic diagram of an anodizing apparatus for performing anodizing treatment.

[0046] First, a substrate 101 made of an Mg-Li alloy that will serve as an anode is prepared (S11). The method for producing the substrate 101 is not particularly limited, but examples thereof include casting, thixomolding, and die-casting. Such a method for obtaining a substrate by rapidly cooling molten metal in a mold can safely and inexpensively obtain a complex-shaped or thin-walled molded body. The substrate may also be obtained by secondary processing such as cutting after rapid cooling in a mold. In addition to the above-mentioned methods, there is also a method for cutting a molded body formed by forging or rolling.

[0047] Next, an anode and a cathode are placed in the electrolytic solution (S12). First, an electrolytic solution 401 to be used for anodization is prepared. The electrolytic solution is a liquid containing fluorine, ammonium, and phosphorus. Examples of substances containing fluorine and ammonium include acidic ammonium fluoride, neutral ammonium fluoride, and ammonia. Examples of substances containing phosphorus include phosphoric acid and ammonium phosphate.

[0048] Here, the content ratio of fluorine ions to the total of phosphate ions and fluorine ions in the electrolyte is in the range of 80% to 99.5%. This is the range that the present inventors found as a result of extensive research. First, by setting the content ratio of fluorine ions in this range, it becomes possible to provide the first recesses 111 and the second recesses 112. Furthermore, within this range, it is easy to make the average equivalent circle diameter R1 of the first recesses larger than 30 μm, and the presence ratio of the first recesses 111 can be set to 5 / mm 2 It has been found that the range is more preferably 85% or more and 99.5% or less, and even more preferably 89% or more and 99.2% or less.

[0049] The ammonium ion concentration in the electrolyte is preferably in the range of 6 mol / L to 12 mol / L. By setting the ammonium ion concentration within this range, the film formation reaction can proceed at a lower voltage than when the concentration deviates from this range. More specifically, a low-resistance film can be formed from the initial growth stage of the anticorrosion film, allowing a film of uniform thickness to be obtained even when the film thickness is greater than 20 μm. On the other hand, if the concentration deviates from this range, high-resistance areas may form from the initial growth stage of the film, resulting in an uneven potential difference within the film. As a result, it becomes difficult to increase the film thickness above the high-resistance areas, which may result in uneven film thickness and poor corrosion resistance or poor appearance. A more preferred ammonium ion concentration is in the range of 6.5 mol / L to 11 mol / L.

[0050] The anodizing device 400 that forms the anodic oxide film is composed of an outer tank 402 that holds and regulates the temperature of the electrolyte, and an inner tank 403 where the electrical reaction occurs. The outer tank 402 is equipped with a temperature regulation mechanism 404 that maintains a constant temperature of the electrolyte. The liquid temperature can be set from a low temperature at which the components do not aggregate to a high temperature at which the components do not decompose. The optimum set temperature is about 25°C, which does not require much energy to regulate the liquid temperature. Although the device configuration is described as a two-tank type, a single-tank type is also acceptable.

[0051] The outer tank 402 and inner tank 403 are connected by a magnetic pump 405, allowing the liquid to circulate. While liquid exchange on the Mg-Li alloy surface is important for the formation of the corrosion-resistant coating 102, the anodization reaction is exothermic, which causes active liquid exchange through self-convection in the electrolyte on the surface. Therefore, the liquid circulation by the pump is more important for removing by-products generated in the electrolyte than for liquid exchange on the surface. During anodization of the Mg-Li alloy surface, lithium in the anode is released as ions into the liquid as the film is formed. These released lithium ions react with fluoride and phosphate ions, which are components of the electrolyte, to form sparingly soluble salts. These sparingly soluble salts may remain in the liquid as fine particles, causing the electrolyte to become cloudy. Therefore, a bag filter 406 is installed at the liquid outlet of the inner tank to remove fine particles generated in the liquid. The filter is preferably capable of removing fine particles larger than 10 μm. A filter may also be installed in the piping system connected to the pump.

[0052] Next, an electrical circuit capable of forming an anticorrosion film is formed. A carbon electrode 407, which functions as a cathode, is installed in the inner tank 403. There are no particular limitations on the material for this cathode, as long as it is stable in the electrolyte and conductive. For example, platinum, stainless steel, titanium, etc. can also be used.

[0053] Next, a substrate made of an Mg-Li alloy is used as the anode 408 and is sandwiched between a conductivity holding jig 409. A natural oxide film is formed on the surface of the anode 408, but this does not need to be removed beforehand as this is replaced by a fluoride film or phosphate film during the anodization process. If the anode has been processed by cutting or other processes and oil stains have adhered to the surface, it is necessary to go through a process such as pre-cleaning to remove the oil stains.

[0054] The material of the conductivity holding jig 409 is a metal that has a higher anodizing voltage than the anode used in anodizing, and is anodized at a high voltage in advance. Materials that can be used include, but are not limited to, pure Mg, AZ31, and AZ91.

[0055] The conduction holding jig 409 sandwiching the anode 408 is connected to a DC stabilized power supply 410 by electric wires so that the jig 409 acts as the anode and the carbon plate acts as the cathode. Furthermore, the conduction holding jig 409 of the cathode connected by electric wires is immersed in the inner tank 403 to establish an anodic oxide film formation circuit.

[0056] Then, a voltage is applied between the anode and cathode to form an anticorrosion film, thereby obtaining an alloy member (S13). First, the stabilized DC power supply 410 is turned on to allow the anodization reaction to proceed. The stabilized DC power supply is set to a maximum current value and is designed not to allow any current beyond that. The voltage during the formation of the anodized film increases as the electrical resistance of the Mg-Li alloy surface increases as the anticorrosion film grows. The temperature of the electrolyte is maintained at a constant level by the function of the temperature control mechanism 404 attached to the device.

[0057] Finally, the timing to stop the current is determined by the cumulative current value passed through the Mg-Li alloy. To give a specific example, the amount of electricity required to grow a film 1 μm thick is 100 cm 2 For example, if the surface area is 100 cm 2 When trying to form a 40 μm anticorrosion film on an Mg-Li alloy anode, turn off the power when 1741 coulombs (43.5 x 40) have been applied.

[0058] Furthermore, the current setting can be determined by the surface area of ​​the anode and the current density. For example, 2 A current density of 5A / 100cm is applied to the anode surface. 2 When anodizing is performed at 10 ... 2 from 10A / 100cm 2By the above method, an alloy member having an anticorrosion film provided on a substrate can be obtained.

[0059] An adhesive is then applied to the anticorrosion coating 102 and / or the members to be joined 104 of the alloy member, followed by curing and joining to obtain a joined body 100 (S14). The adhesive is preferably applied so as to wet and spread over the entire surface 102A of the anticorrosion coating 102. That is, the adhesive is preferably applied so as to wet and spread over the first recesses 111, the second recesses 112, and the regions 102AA of the anticorrosion coating 102 other than the recesses. When cured, the adhesive becomes the joining resin 103. The type of adhesive is not particularly limited, but solvent-free adhesives using urethane resin or epoxy resin can be used. In this case, the viscosity of the adhesive is in the range of 5 Pa·s to 100 Pa·s. Even with such a high viscosity adhesive, the anchoring effect can be achieved as long as the first recesses are larger than 30 μm. The method of applying the adhesive is not particularly limited, but when using a two-component adhesive, it is preferable to apply a fixed amount using a dispenser. The members to be joined 104 are bonded to the adhesive-coated surface of the anticorrosion coating 102. After bonding, the adhesive is gently pressed against the adhesive-coated surfaces to ensure that the adhesive adheres to them. Finally, the adhesive is cured to obtain the bonded structure of the present disclosure. Depending on the type of adhesive, the adhesive may be left at 60°C for 30 minutes or left at room temperature for at least half a day until it is completely cured.

[0060] As described above, the manufacturing method of the joined body of the present disclosure uses an electrolyte in which the ratio of fluorine ions to the total of phosphate ions and fluorine ions is in the range of 88% to 99.5% when anodizing the alloy substrate. This allows the formation of first and second recesses in the anticorrosion film. The alloy member having the anticorrosion film and the joined member are joined via an adhesive, thereby providing a joined body with superior adhesive strength compared to conventional methods.

[0061] <Modification of the first embodiment> Next, an example in which the bonded body of the first embodiment is applied to an apparatus will be described. An X-ray apparatus will be described below as an example, but the apparatus is not limited to this.

[0062] [Radiation X-ray equipment] Fig. 6(a) is a view of a radiographic apparatus 500, which is an example of an apparatus, as viewed from the side of a radiation incident surface portion where radiation R is incident. As shown in Fig. 6(a), the radiographic apparatus 500 is configured to have an exterior part 501. This exterior part 501 includes a radiation transparent plate 520 that constitutes the radiation incident surface portion described above and allows radiation R to pass through, a rear housing 530 that constitutes a rear part facing the radiation transparent plate 520, a frame body 510 that is a frame-shaped member that constitutes a side part located between the radiation transparent plate 520 and the rear housing 530, and a bonding resin 540.

[0063] The alloy member 105 of the first embodiment can be applied to the frame body 510. Similarly, the member to be joined 104 of the first embodiment can be applied to the radiation transparent plate 520 and / or the rear housing 530. In FIG. 6(a) and FIG. 6(b) and FIG. 7 described below, a bonding resin 540 is provided between the frame body 510 and the radiation transparent plate 520, and the frame body 510 and the radiation transparent plate 520 are bonded together via the bonding resin 540. The radiation transparent plate 520 is an example of a plate-like member. A bonding resin 540 is provided between the frame body 510 and the rear housing 530, and the frame body 510 and the rear housing 530 are bonded together via the bonding resin 540. The rear housing 530 is an example of a plate-like member.

[0064] Fig. 6(b) is a view of the radiation imaging device 500 as seen from the rear side, which faces the radiation incident surface onto which radiation R is incident. That is, the view is of the radiation imaging device 500 as seen from the rear housing 530 side. In Fig. 6(b), a wireless radio wave transparent window 511 and a wireless radio wave transparent window 531 are provided on one side of the frame 510 and at predetermined positions on the rear housing 530, respectively, to enable wireless communication. Fig. 6(b) also illustrates the power supply 14 contained in the exterior part 501.

[0065] The exterior casing 501 of the radiographic imaging device 500 is required to be made of a lightweight, strong material. An Mg-Li alloy is preferable for the frame 510. This is because it is lighter and has better vibration damping and specific strength than magnesium alloys that do not contain lithium. Furthermore, it is preferable to select a material for the radiation-transmitting plate 520 that has good transmittance for the incident radiation R. For example, carbon fiber reinforced plastic (CFRP), carbon, polyvinyl chloride, acrylic, polyester, or polymethyl methacrylate resin (PMMA) can be used for the radiation-transmitting plate 520. For example, an Mg-Li alloy, an Mg alloy, an Al alloy, or a carbon fiber reinforced plastic (CFRP) can be used for the rear housing 530. When an Mg-Li alloy is used for the rear housing 530, the frame 510 and the rear housing 530 can be integrally formed. In this case, no bonding resin is required.

[0066] Fig. 7 is a diagram showing an example of a schematic configuration of the radiographic apparatus 500 shown in Fig. 6(b) at cross section II. In Fig. 7, the same components as those shown in Fig. 6 are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0067] A phosphor layer 4 that converts radiation R transmitted through the subject into light is laminated inside the exterior casing 501 of the radiographic imaging device 500. The phosphor layer 4 and the radiation detection unit 5 convert the light generated by the phosphor layer 4 into an electrical signal. Specifically, the phosphor layer 4 and the radiation detection unit, which are examples of components, are arranged in a space surrounded by a frame 510, a radiation-transmitting plate 520 that is a plate-shaped member, and / or a rear housing 530. The phosphor layer 4 and the radiation detection unit 5 constitute a radiation detector that converts radiation transmitted through the subject into an electrical signal. The radiation detection unit 5 is attached to a sensor holding plate 7 via a radiation-shielding member 6. GOS (Gd2O2S) or CsI is commonly used as the material for the phosphor layer 4. The radiation detection unit 5 is generally formed using a glass substrate, and therefore is susceptible to cracking when subjected to strong impacts, loads, or displacements. Therefore, an impact-absorbing member 8 is arranged on the radiation entrance surface of the radiation detection unit 5 in the radiographic imaging device 500 to absorb impacts. The shock absorbing member 8 must be made of a material with high radiation transmittance in order to guide the radiation R that has passed through the subject to the phosphor layer 4 without attenuating it as much as possible. The radiation shielding member 6 has the function of protecting the electric board 12 and other components from the radiation R that has passed through the subject and the radiation detection unit 5. In addition, the radiation shielding member 6 has the function of preventing the radiation R that has passed through the radiographic imaging device 500 and been scattered by a wall or the like behind it from bouncing back and re-entering the phosphor layer 4 or the radiation detection unit 5. For this reason, materials such as Mo, W, Pb, Al, Cu, SUS, and barium sulfate are often used as materials for the radiation shielding member 6, and a sheet material containing a mixture of these materials may also be used.

[0068] On the surface of the sensor holding plate 7 facing the rear housing 530, there are installed an electric board for reading out the electric signals converted by the radiation detection unit 5 via the wiring 11, an electric board and a communication module board for generating image data of the radiation image after reading out the electric signals, an antenna for wireless communication, etc.

[0069] When wireless communication is performed, if exterior part 501 is made of a metallic material, wireless radio waves are blocked, so exterior part 501 is provided with wireless radio wave transmitting window 511 and wireless radio wave transmitting window 531 as shown in Fig. 7. Antenna 13 is placed in a position close to these wireless radio wave transmitting windows 511 and 531 in consideration of the radio radiation characteristics. Furthermore, wireless radio wave transmitting window 511 and wireless radio wave transmitting window 531 may be integrated across adjacent side surfaces of exterior part 501.

[0070] Since the joined structure 100 of the first embodiment has excellent adhesive strength, the adhesive area can be made smaller than that of conventional structures, and therefore, when the frame body 510 and the radiation transmitting plate 520 and / or the rear housing 530 are joined with a bonding resin, it is possible to provide a smaller and lighter radiation imaging device 500 with a narrower frame width. The joined structure 100 of the first embodiment can be used not only for the exterior part 501 but also for the sensor holding plate 7.

[0071] Second Embodiment 8 is a schematic diagram of an alloy member according to the second embodiment, showing a cross section cut in the stacking direction. The alloy member 200 includes a substrate 101, an anticorrosion film 102 provided on the substrate 101, and a resin film 203, which is a cured resin provided on the anticorrosion film 102. The alloy member 200 of the second embodiment differs from the joined body 100 of the first embodiment in that it does not include the joining resin 103 and the joined members 104, but does include the resin film 203.

[0072] The use of the alloy member 200 is not particularly limited, and it can be used as a structure according to the user's use, such as an exterior member (casing) of a device having parts, an interior member, or a sliding member.

[0073] In the following, the same components as those shown in FIG. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0074] (resin film) The resin film 203 is a coating film such as a primer or a topcoat layer. Examples of the coating film include a heat-shielding film having a heat-shielding function, a sliding film having abrasion resistance, a light-shielding film having light-shielding and light-absorbing properties, and a weather-resistant film that extends the service life of equipment and devices.

[0075] As with the bonding resin 103 of the bonded structure of the first embodiment, the resin film 203 is provided with a portion in the first recess 111 and the second recess 112, thereby enhancing adhesion between the anticorrosion coating 102 and the resin film 203. Therefore, the alloy member 200 having the resin film 203 has excellent adhesion of the resin film 203. This is because, when an uncured resin material, which is a precursor of the resin film 203, is placed on the anticorrosion coating 102, the uncured resin material penetrates into the first recess 111 and the second recess 112 and cures. That is, the resin film 203 contacts the region 102AA of the surface 102A other than the recesses, the surface 111A of the first recess, and the surface 112A of the second recess. Since the alloy member 200 has the second recess 112, the contact area between the corrosion-resistant film 102 and the resin film 203 is increased compared to when the alloy member does not have the second recess 112, and as a result, the adhesion between the corrosion-resistant film 102 and the bonding resin 103 is stronger than in an alloy member that does not have the second recess 112.

[0076] The material of the resin film 203 is not particularly limited, but may be, for example, a urethane resin or an epoxy resin. The viscosity of the uncured resin material that is the precursor of the resin film 203 is in the range of 0.01 Pa·s to 0.1 Pa·s.

[0077] The elastic modulus of the resin film 203 is preferably in the range of 0.1 GPa to 15 GPa. If the elastic modulus is in this range, the resin film 203 can absorb the impact even if the alloy member 200 is dropped, and peeling between the resin film 203 and the anticorrosion film 102 is unlikely to occur. The elastic modulus is more preferably in the range of 0.2 GPa to 5 GPa.

[0078] The thickness of the resin film 203 is preferably in the range of 3 μm to 150 μm. Even if the alloy member 200 is dropped, the impact is absorbed and peeling between the resin film 203 and the anticorrosion film 102 is unlikely to occur. A more preferable thickness is in the range of 5 μm to 50 μm.

[0079] <Modification of the second embodiment> Next, an example in which the alloy member of the second embodiment is applied to a device will be described. While an interchangeable lens and a single-lens reflex digital camera will be described as examples, the device is not limited to these and may also be a smartphone or a compact digital camera.

[0080] [Optical equipment / imaging devices] Fig. 9 shows the configuration of a single-lens reflex digital camera 600, which is an example of an imaging device. In Fig. 9, a camera body 602 is coupled to a lens barrel 601, which is an optical device. The lens barrel 601 is a so-called interchangeable lens that can be attached to and detached from the camera body 602.

[0081] Light from a subject is received by an imaging element after passing through an optical system consisting of multiple lenses 603, 605, which are an example of components arranged on the optical axis of the photographic optical system inside the housing of lens barrel 601. Here, lens 605 is supported by an inner barrel 604, and is supported movably relative to the outer barrel of lens barrel 601 for focusing and zooming.

[0082] During the observation period before shooting, light from the subject is reflected by a main mirror 607, which is an example of a component inside a camera body housing 621, passes through a prism 611, and then is projected to the photographer through a viewfinder lens 612 as a shot image. The main mirror 607 is, for example, a half mirror, and the light that passes through the main mirror is reflected by a sub-mirror 608 toward an AF (autofocus) unit 613. This reflected light is used, for example, for distance measurement. The main mirror 607 is attached and supported by a main mirror holder 640, for example, by adhesive. During shooting, a drive mechanism (not shown) moves the main mirror 607 and sub-mirror 608 out of the optical path, opens a shutter 609, and forms a shot light image incident from the lens barrel 601 on an image sensor 610. The aperture 606 is configured so that the brightness and depth of focus during shooting can be changed by changing the opening area.

[0083] The alloy member 200 can be used for at least a part of the housings 620, 621, and in this case, the resin film 203 is arranged so as to be provided on at least a part of the outer periphery of the housings 620, 621. Since the alloy member 200 has excellent adhesion between the anticorrosion film 102 and the resin film 203, it is possible to provide a lightweight imaging device with superior adhesion strength of the resin film compared to conventional imaging devices. [Example]

[0084] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples.

[0085] Example 1 [Manufacturing of alloy components] First, a substrate made of a magnesium-lithium alloy was prepared as the anode for the anodization device. A cylindrical billet (90 mm in bottom diameter, 300 mm in length) of Ares (composition: Mg-9%Li-4%Al-1%Zn, manufactured by Anritsu Materials Technology Co., Ltd.) was prepared as the raw material. This cylindrical billet was placed in the material supply device of a die-casting molding machine (Sodick LMI450) and forced into the melting cylinder for melting. The molten metal was fed into the injection cylinder and extruded into a mold at high speed using an injection plunger. The molding conditions were a mold temperature of 200°C and an injection speed of the molding machine of 2000 mm / s. A portion of the solidified compact in the mold was cut into a rectangular parallelepiped measuring 40 mm × 14 mm × 4 mm, and each face of the rectangular parallelepiped was lapped and polished to form the substrate 101 of Example 1.

[0086] Next, an anode and a cathode were placed in the electrolyte. The anode was the substrate 101 described above. The electrolyte 401 was prepared by adding pure water to 4600 g of ammonium fluoride and 1900 g of triammonium phosphate trihydrate, so that the volume was 20 liters when completely dissolved. The electrolyte 401 had a fluorine ion content of 6.2 mol / L, a phosphate ion content of 0.47 mol / L, and an ammonium ion content of 7.6 mol / L. The electrolyte was poured into the outer tank of the anodization apparatus 400 shown in Figure 4, and the magnetic pump 405 was started. After the liquid in the inner tank overflowed and liquid circulation began, the temperature control mechanism 404 was started to stabilize the liquid temperature at 20°C. Furthermore, a carbon plate functioning as a cathode was immersed in the inner tank and connected to the cathode of the power supply via a lead wire.

[0087] Next, a voltage was applied between the anode and cathode to form a corrosion-resistant film 102, resulting in the alloy component. Specifically, a continuity holding jig 409 made of AZ31 material was first prepared. The substrate continuity holding jig had a fixed hinge at the tip of an AZ31 round bar and a movable hinge located 107 mm from the fixed hinge. The fixed and movable hinges were configured to contract using Viton O-rings. This substrate continuity holding jig was previously anodized in the above electrolyte until no current flowed at a voltage of 140 V. This treatment facilitates power transmission to the substrate continuity holding jig. The substrate to be anodized was sandwiched between the pre-treated substrate continuity holding jig, connected to the anode of the power supply via a lead, and immersed in the inner tank facing the cathode. A PAT160-100TMX manufactured by Kikusui Electronics Co., Ltd. was used as a DC regulated power supply 410. The input current is 0.78A (surface area: 15.5cm 2 , Current density: 5A / 100cm 2 The target film thickness was set to 45 μm, and the applied current was set to 408 coulombs. When the specified amount of coulombs was reached, the current from the DC stabilized power supply was stopped.

[0088] The substrate and the substrate continuity holding jig after the anodization treatment were removed from the inner tank and rinsed with pure water to thoroughly wash away the electrolyte adhering to the surface. The substrate was then dried in a clean oven at 60°C to obtain the alloy member of Example 1. The thickness of the anticorrosion film was 47.4 μm.

[0089] [Manufacturing of joints] Two alloy members of Example 1 were prepared. An adhesive (product name: two-component epoxy strong adhesive, manufactured by Daiso Industries Co., Ltd.) was applied to the surface 102A of the anticorrosion coating of one alloy member and the surface 112A of the first recess (40 mm × 14 mm in plan view). The adhesive's main agent was epoxy resin, and the curing agent was a modified amine. The adhesive's main agent and curing agent were thoroughly mixed, and 0.5 ml of the adhesive was applied. The other alloy member was used as the member to be joined 104. The member to be joined 104 was then bonded and pressed against the alloy member to which the adhesive had been applied. The adhesive was then cured in a clean oven at 60°C, yielding a bonded body of Example 1.

[0090] (Examples 2 to 5 and Comparative Examples 1 to 3) Examples 2 to 5 differ in that the contents of ammonium fluoride and triammonium phosphate trihydrate were changed, and the electrolyte was adjusted to have the fluorine ion ratio shown in Table 1. Alloy members and joined bodies were produced using the same procedures as in Example 1 in all other respects.

[0091] [Table 1]

[0092] [Evaluation of alloy components] The proportion of first recesses 111 present on the surface 102A of the anticorrosion coating of the alloy members of the example and comparative example was measured. The measurement method was to obtain an SEM image at a magnification of 50 times, and measure a 1 mm 2The number of first recesses 111 with an opening diameter T within this range was measured in five fields of view, and the average value was taken as the abundance ratio. SEM images were taken using a Sigma500VP (FE-SEM) device manufactured by ZEISS. In addition, the number of hole-like second recesses 112 that were present on the side walls of the first recesses 111 and could be observed from the surface 102A side of the anticorrosion coating 102 was visually counted.

[0093] [Evaluation of zygotes] <Adhesive strength> The adhesive strength of the joined bodies of the example and comparative example was evaluated. The evaluation method will be explained using Figure 10. One side of the alloy member 105 of the joined body of Example 1 was fixed, and a load P was applied to the unfixed joined member 104 in a direction parallel to the bonding surface of the bonding resin 1-3. The load and displacement were measured from the initial application of the load P until the bonding surface broke.

[0094] The maximum load was multiplied by the displacement to determine the value. If the value was 8.0 MPa·mm or more, it was rated A; if it was 5.0 MPa·mm or more but less than 8.0 MPa·mm, it was rated B; if it was 4.5 MPa·mm or more but less than 5.0 MPa·mm, it was rated C; and if it was less than 4.5 MPa·mm, it was rated D. A, B, and C were judged to be good.

[0095] <Observation of fracture surface> The adhesive surface of the broken bonding resin was observed at magnifications of 30 to 3000 times using an FE-SEM (manufactured by ZEISS).

[0096] Using the fractured joint, the surface 102A of the anticorrosion film was subjected to elemental analysis by EDS at a magnification of 3000 times using a Sigma500VP (FE-SEM) manufactured by ZEISS.

[0097] Table 2 shows the evaluation results of the proportion of fluorine ions, the proportion of first recesses present, and adhesive strength.

[0098] [Table 2]

[0099] From Table 2, it can be seen that Examples 1 to 5, in which the fluorine ion content was in the range of 88% or more and 99.5% or less, had sufficient adhesive strength. On the other hand, Comparative Examples 1 to 3, in which the fluorine ion content did not satisfy the above range, had insufficient adhesive strength.

[0100] Although not shown in Table 2, the number of second recesses in Example 1 varied depending on the size of the first recesses 111, with a minimum of 5 and a maximum of 33, and an average of 13. In the other Examples as well, the number of second recesses was a minimum of 5 and a maximum of 33.

[0101] Next, elemental analysis was performed on the fracture surface of the anticorrosion coating 102 of Example 2 at a magnification of 3000x. FIG. 12 shows an SEM-EDS image of the surface 102A of the anticorrosion coating of Example 2. The elements analyzed by EDS were Mg, P, F, O, and C. FIG. 12(a) shows an SEM image of the composition, and the images shown in (b) to (f) show the abundance ratio of each element, i.e., Mg, P, F, O, and C, respectively. Higher percentages of each element are displayed in white, and lower percentages are displayed in black. The analysis conditions were an acceleration voltage of 10 kV and a work distance of 8.0 mm to 8.5 mm. The flat surface 301 in the SEM image is the fracture surface where the anticorrosion coating was destroyed, and the spherical rough surfaces 302 are the surfaces of the first recesses 111 and the second recesses 112. The EDS analysis results revealed that the rough surfaces 302, which were the surfaces of the first recesses and the second recesses, had a higher F concentration than other areas. Furthermore, an organic layer 303 containing C component derived from the adhesive was confirmed on the surface in contact with the rough surface 302. This confirms that the outermost surfaces of the first and second recesses are fluoride layers. This suggests that the non-stickiness (liquid repellency) of fluorine allows the adhesive to penetrate deeper and harden / solidify. This allows the adhesive to penetrate into more complex shapes, and it is presumed that the "return effect" improves adhesive strength. Because the observation area was the center of the cross-section of the anticorrosion film, it was found that the adhesive had penetrated to a depth of approximately 20 μm from the surface where the adhesive was applied in the cross-section of the anticorrosion film.

[0102] As described above, it has been found that the adhesive strength can be improved by providing the first recess and the second recess. [Industrial Applicability]

[0103] The alloy member and joined body according to the present disclosure can be used as structures for medical devices such as radiographic devices, and optical devices such as lens barrels and camera bodies, as well as for various electronic devices such as personal computers, mobile objects such as drones, and other industrial equipment.

[0104] The present disclosure includes the following:

[0105] (Section 1) a substrate containing magnesium and lithium; An alloy member comprising: an anticorrosion film provided on the substrate and containing magnesium, phosphorus, and fluorine, the anticorrosion coating has at least one first recess on a surface opposite to the substrate; the surface of the first recess has at least one second recess smaller than the first recess; An alloy member characterized by:

[0106] (Section 2) Item 2. The alloy member according to item 1, wherein the first recesses have an average equivalent circle diameter of 30 μm or more.

[0107] (Section 3) Item 3. The alloy member according to item 1 or 2, wherein the second recesses have an average equivalent circle diameter of 10 μm or less.

[0108] (Section 4) 4. The alloy member according to any one of items 1 to 3, wherein a first normal to a virtual plane filling the first recess and a second normal to a virtual plane filling the second recess intersect.

[0109] (Section 5) 5. The alloy structural member according to any one of items 1 to 4, wherein the distance between the adjacent first recesses is equal to or greater than the average equivalent circle diameter of each of the adjacent first recesses.

[0110] (Section 6) 6. The alloy member according to any one of items 1 to 5, wherein the fluorine content on the surface of the first recess and the surface of the second recess is greater than the fluorine content on the surface of the anticorrosion film in a region other than the first recess and the second recess.

[0111] (Section 7) 7. The alloy member according to any one of items 1 to 6, wherein the anticorrosion film has a thickness of 20 μm or more.

[0112] (Section 8) 8. The alloy member according to any one of items 1 to 7, wherein the sum of the magnesium content and the lithium content in the substrate is 90 mass % or more.

[0113] (Section 9) Item 9. The alloy member according to item 8, wherein the lithium content in the substrate is in the range of 0.5% by mass to 15% by mass.

[0114] (Section 10) Item 10. The alloy member according to item 9, wherein the content of lithium in the substrate is in the range of 5% by mass to 11% by mass.

[0115] (Section 11) the substrate contains aluminum; Item 11. The alloy member according to any one of Items 8 to 10, wherein the aluminum content in the base material is in the range of 1% by mass to 8% by mass.

[0116] (Section 12) the substrate contains germanium and / or beryllium; Item 12. The alloy member according to any one of items 8 to 11, wherein the content of germanium and / or beryllium in the base material is in the range of 0.02% by mass to 0.4% by mass.

[0117] (Section 13) In the substrate, The germanium content is in the range of 0.04% by mass or more and 0.4% by mass or less, Item 13. The alloy member according to item 12, wherein the beryllium content is in the range of 0.02% by mass to 0.1% by mass.

[0118] (Section 14) the substrate contains zirconium; Item 14. The alloy structural member according to any one of Items 8 to 13, wherein the zirconium content in the base material is 0.6% by mass or more and 3.0% by mass or less.

[0119] (Section 15) the substrate contains at least one element selected from the group consisting of zinc, calcium, silicon, and manganese; Item 15. The alloy structural member according to any one of Items 8 to 14, wherein the sum of the contents of the elements in the group in the base material is in the range of 0.01% by mass to 5% by mass.

[0120] (Section 16) The zinc content is 3% by mass or less, The calcium content is 3% by mass or less, The silicon content is 0.2% by mass or less, The manganese content is 0.5% by mass or less, Item 16. The alloy member according to item 15, wherein the balance is inevitable impurities and the magnesium.

[0121] (Section 17) Item 17. The alloy member according to any one of items 1 to 16, further comprising a resin film on the anticorrosion film.

[0122] (Section 18) A joined body comprising the alloy members according to any one of items 1 to 16, members to be joined, and a joining resin that joins the alloy members and the members to be joined, A bonded body, characterized in that a part of the bonding resin is provided in the first recess and the second recess.

[0123] (Section 19) the alloy member is a frame-shaped member, Item 19. The joined body according to item 18, wherein the members to be joined are plate-like members.

[0124] (Section 20) Item 20. An apparatus comprising the bonded body according to item 19 and a part, characterized in that the part is provided in a space surrounded by the frame-shaped member and the plate-shaped member.

[0125] (Section 21) An apparatus comprising a housing and a component within the housing, Item 18. A device characterized in that the housing includes the alloy member according to item 17, and the resin film is provided on at least a part of the outer periphery of the housing.

[0126] (Section 22) placing an anode and a cathode in an electrolyte; and applying a voltage between the anode and the cathode to form an anticorrosion film on the anode, the anode contains magnesium and lithium; the electrolyte contains fluorine, ammonium, and phosphorus; A method for producing an alloy member, wherein the content of fluorine ions in the electrolyte is in the range of 88% to 99.5% of the total of phosphate ions and fluorine ions.

[0127] (Section 23) placing an uncured resin material on the anticorrosion film; Item 23. The method for producing an alloy member according to item 22, further comprising: curing the uncured resin material to form a resin film.

[0128] (Section 24) Item 24. The method for producing an alloy member according to Item 23, wherein the viscosity of the uncured resin material is in the range of 0.01 Pa·s to 0.1 Pa·s.

[0129] (Section 25) A method for manufacturing a joined body in which an alloy member and a joined member are joined via an adhesive, comprising the steps of: Item 22. A step of preparing an alloy member by the method described in item 22; placing an adhesive on the alloy members and / or the members to be joined; and a step of hardening the adhesive to form a bonding resin that bonds the alloy member and the member to be bonded.

[0130] (Section 26) Item 26. The method for producing a bonded body according to Item 25, wherein the adhesive has a viscosity in the range of 5 Pa·s to 100 Pa·s.

[0131] (Section 27) A corrosion-resistant film containing magnesium, phosphorus, and fluorine, the anticorrosion coating has at least one first recess on a surface opposite to the substrate; the surface of the first recess has at least one second recess smaller than the first recess; A corrosion prevention film characterized by: [Explanation of symbols]

[0132] 100 zygote 101 Base material 102 Anticorrosion film 103 Bonding resin 104 Parts to be joined 105 alloy components 111 first recess 112 Second recess 200 Alloy components 203 Resin Film

Claims

1. a substrate containing magnesium and lithium; An alloy member comprising: an anticorrosion film provided on the substrate and containing magnesium, phosphorus, and fluorine, the anticorrosion coating has at least one first recess on a surface opposite to the substrate; a surface of the first recess having at least one second recess smaller than the first recess; An alloy member characterized by:

2. 2. The alloy member according to claim 1, wherein the first recesses have an average equivalent circle diameter of 30 μm or more.

3. 2. The alloy member according to claim 1, wherein the second recesses have an average equivalent circle diameter of 10 μm or less.

4. The alloy member according to claim 1 , wherein a first normal to an imaginary plane filling the first recess and a second normal to an imaginary plane filling the second recess intersect with each other.

5. 2. The alloy member according to claim 1, wherein the distance between adjacent first recesses is equal to or greater than the average equivalent circle diameter of each of the adjacent first recesses.

6. The alloy member according to claim 1, wherein the fluorine content on the surface of the first recess and the surface of the second recess is greater than the fluorine content in regions of the surface of the corrosion protection film other than the first recess and the second recess.

7. 2. The alloy member according to claim 1, wherein the anticorrosion film has a thickness of 20 μm or more.

8. 2. The alloy member according to claim 1, wherein the sum of the magnesium content and the lithium content in the substrate is 90 mass % or more.

9. The alloy member according to claim 8, wherein the content of the lithium in the substrate is in the range of 0.5% by mass to 15% by mass.

10. The alloy member according to claim 9, wherein the content of the lithium in the substrate is in the range of 5% by mass to 11% by mass.

11. the substrate contains aluminum; The alloy member according to claim 8, wherein the content of the aluminum in the base material is in the range of 1 mass % to 8 mass %.

12. the substrate contains germanium and / or beryllium; 9. The alloy member according to claim 8, wherein the content of the germanium and / or beryllium in the base material is in the range of 0.02 mass % to 0.4 mass %.

13. In the substrate, The germanium content is in the range of 0.04 mass% or more and 0.4 mass% or less, 13. The alloy structural member according to claim 12, wherein the beryllium content is in the range of 0.02 mass % to 0.1 mass %.

14. the substrate contains zirconium; The alloy structural member according to claim 8, wherein the zirconium content in the base material is 0.6 mass % or more and 3.0 mass % or less.

15. the substrate contains at least one element selected from the group consisting of zinc, calcium, silicon, and manganese; 9. The alloy member according to claim 8, wherein the sum of the contents of the elements in the group in the base material is in the range of 0.01% by mass to 5% by mass.

16. The zinc content is 3% by mass or less, The calcium content is 3% by mass or less, The silicon content is 0.2 mass% or less, The manganese content is 0.5% by mass or less, The alloy member according to claim 15, wherein the balance is inevitable impurities and the magnesium.

17. The alloy member according to claim 1 , further comprising a resin film on the anticorrosion film.

18. A joined body comprising the alloy member according to any one of claims 1 to 16, members to be joined, and a joining resin that joins the alloy member and the members to be joined, A bonded body, characterized in that a part of the bonding resin is provided in the first recess and the second recess.

19. the alloy member is a frame-shaped member, 19. The joined body according to claim 18, wherein the members to be joined are plate-like members.

20. 20. An apparatus comprising the joined body according to claim 19 and a component, wherein the component is provided in a space surrounded by the frame-shaped member and the plate-shaped member.

21. An apparatus comprising a housing and a component within the housing, 18. An apparatus, wherein the housing includes the alloy member according to claim 17, and the resin film is provided on at least a portion of the outer periphery of the housing.

22. placing an anode and a cathode in an electrolyte; and applying a voltage between the anode and the cathode to form an anticorrosion film on the anode, the anode contains magnesium and lithium; the electrolyte contains fluorine, ammonium, and phosphorus; The method for producing an alloy member, wherein the content of fluorine ions in the electrolyte is in the range of 88% to 99.5% of the total of phosphate ions and fluorine ions.

23. placing an uncured resin material on the anticorrosion film; The method for manufacturing an alloy member according to claim 22, further comprising: curing the uncured resin material to form a resin film.

24. The method for manufacturing an alloy member according to claim 23, wherein the viscosity of the uncured resin material is in the range of 0.01 Pa·s to 0.1 Pa·s.

25. A method for manufacturing a joined body in which an alloy member and a joined member are joined via an adhesive, comprising the steps of: providing an alloy component according to the method of claim 22; placing an adhesive on the alloy member and / or the member to be joined; and a step of hardening the adhesive to form a bonding resin that bonds the alloy member and the member to be bonded.

26. 26. The method for manufacturing a joined body according to claim 25, wherein the viscosity of the adhesive is in the range of 5 Pa·s to 100 Pa·s.

27. A corrosion-resistant film containing magnesium, phosphorus, and fluorine, the anticorrosion coating has at least one first recess on a surface opposite to the substrate; a surface of the first recess having at least one second recess smaller than the first recess; A corrosion prevention film characterized by:

Images