Manufacturing processes for metallic parts and the metallic part

Abstract

A manufacturing method for metallic parts, the method comprising:immersing a metallic material in a metal bath of a first component, the metallic material comprising a second component having a positive heat of mixing relative to the first component and a third component having a negative heat of mixing relative to the first component, and the metallic material consisting of a chemical compound, an alloy, or a nonequilibrium alloy having melting points above the freezing point of the metallic bath;Selectively dissolving the third component in the metal bath to form a metallic part with extremely fine interstices, the selective dissolving being achieved by:controlling the metal bath so that its temperature is lower than the minimum liquidus temperature within the compositional variation range in which the proportion of the third component in the metallic material ranges from the original proportion to no proportion;

Description

[Technical field]

[0001] This invention relates to the method of manufacture for a metallic material and the metallic material having tiny pores on its surface or everywhere. [Technical background]

[0002] The attempt to enhance the value of metallic materials by making them porous was undertaken over half a century ago. Porous metals are expected to be extremely versatile, suitable for applications such as extremely lightweight materials, materials with high specific hardness, energy-absorbing materials, vibration-absorbing materials, sound-insulating materials, thermal insulation materials, electrode materials, filter materials, medical materials, heat exchanger materials, and materials for oil-bearing bearings; their potential to provide solutions in environmental protection, the energy sector, and addressing the challenges of aging is also significant.

[0003] Expectations are particularly high for porous metallic materials with tiny pores in the nanometer range, with a pore size of less than 1 μm. Because such materials have a much larger surface area compared to solid metal bodies, their catalytic properties, electrode characteristics, gas storage capacity, and sensory properties are functionally unattainable with conventional materials. To date, the following methods, for example, have been used to produce porous metals: foam melting, gas expansion, precursor methods, heat synthesis, high-temperature synthesis, deposition, and spacer methods. The pores produced by these methods all have a size of several tens of micrometers; reducing their size further is not easily achieved.Therefore, porous metals with a pore size in the nanometer range were mainly produced using the alloy dissolution method described below.

[0004] In the alloy dissolution method, a porous body is produced by dissolving and removing only the main component of the base metal from alloys or chemical compounds – which are characterized by having as their main component a composite layer of a base and a noble metal, whose standard electrode potential is either negative or positive – at room temperature in an acidic or alkaline aqueous solution; what remains in the layer is a porous structure of the noble metal (see e.g. patent literature 1).

[0005] In recent years, metallic materials have also gained attention as medical materials. Advances in medicine mean that people are living longer; consequently, the age-related impairments and functional losses of all organs will become increasingly severe in the future, making the restoration of these functions an extremely important task. One effective way to address this challenge is the development of medical devices that utilize ceramics, macromolecules, or metallic materials.Examples include, broadly categorized as: devices for plastic surgery, such as artificial joints or materials for stabilizing bones; devices for internal medicine and surgery of circulatory organs, such as implanted artificial hearts or stains in veins; devices for the nose and ear department, such as artificial inner and middle ears; devices in dentistry, such as implants or orthodontic wires; and devices for general surgery, such as catheters or surgical instruments.

[0006] Metallic materials excel in terms of their malleability and machinability, their superelasticity, and their shape memory; they are also superior to ceramics and macromolecules in terms of stability and toughness. Therefore, approximately 80% of devices implanted in the body that cannot be replaced by ceramics or macromolecules are designed using metallic materials. SUS316L stainless steel (an austenitic stainless steel), Ti-6Al-4V ELI, cobalt-chromium alloys (Co-Cr), Ti-6Al-4Nb, nickel-free stainless steel, and Nitinol (a shape memory alloy of titanium and nickel (Ti-Ni) with a nickel content between 48.5% and 51.5%) are all well-known metallic materials used in medical devices.

[0007] While metallic materials used in medical devices are important for their stability and toughness, they also present challenges that must be overcome. Typically, metallic materials ionize and dissolve through corrosion when they come into contact with living tissue, posing a risk of poisoning. Therefore, high corrosion resistance is essential for their use in medical devices. Known allergenic metals include nickel, mercury, cobalt, palladium, and chromium, with nickel allergies being particularly severe. Nickel has also been identified as a carcinogen, leading to the establishment of elution standards in all countries as a countermeasure.Subsequently, alloy development was pursued under the premise that alloys for medical devices should no longer contain nickel; however, this restriction is a major obstacle for alloy development, and progress is currently slow.

[0008] To solve this problem, surface treatment processes exist (see patent literature 2 and 3); these use electrolytic aqueous solutions; they dissolve the nickel from the surface of the alloy containing nickel, creating a film consisting essentially of titanium oxide with a reduced nickel concentration; this suppresses the release of nickel ions into the body. [Literature on the state of the art][Patent literature]

[0009] [Patent Literature 1] Japanese translation of PCT application no. 2008-509742 [Patent Literature 2] International Publication No. 2007 / 018189 [Patent Literature 3] Unexamined publication of patent application no. 2007-6941 [Overview of the invention][Problems that this invention solves]

[0010] For the alloy dissolution method described in patent literature 1, successes have been reported for making noble metals such as gold or platinum porous with nanometer-sized pores; however, it is fundamentally impossible to make base metals porous with a nanometer-sized pore size, so consequently, no success report exists in this regard. Therefore, the problem remained of producing a porous material with nanometer-sized pores using the alloy dissolution method with materials that have excellent mechanical and functional properties, such as Ti, Zr, Ni, Cr, Mo, and W – because their standard electrode potential is negative.

[0011] In the surface treatment processes described in patent literature 2 and 3, the nickel concentration could be reduced in a layer thickness of a few hundred nanometers from the surface; however, the titanium oxide that forms as an oxide layer on the surface is usually brittle, and its elastic limit bending is reduced compared to the metallic substrate. Therefore, when the substrate is deformed, cracks appear in the oxide layer at the surface, creating a risk that nickel ions, which are allergens, will be leached out from the exposed substrate; thus, there is still a problem with biocompatibility.

[0012] This invention was made with this problem in mind; it was intended to provide a manufacturing process for metallic materials or a metallic material itself, in which porous bodies with a pore size in the nanometer range can be easily produced from base metals. Furthermore, the mechanical properties of the overall material should not be impaired; the aim was to provide a manufacturing process for metallic materials or a metallic material itself that possesses excellent biocompatibility and suppresses the leaching of nickel ions. [Means to solve the problems]

[0013] A manufacturing process for metallic materials according to this invention, which serves to achieve the above-described objective, is characterized by the following points: a metallic material consisting of a chemical compound, an alloy, or a non-equilibrium alloy is immersed in a metal bath consisting of the first component; the metallic material contains the second and third components, which have a positive or negative effect on the first component.They have negative heats of mixing; furthermore, their melting points are above the freezing point of the metal bath; the metal bath is controlled in such a way that the third component in the metallic material decreases and that its temperature is lower than the minimum value of the liquidus curve temperature, within the composition variation range until the second component is reached; this allows the third component to be selectively dissolved in the metal bath and a metallic material with very fine interstitial spaces is obtained.

[0014] The manufacturing process for metallic materials according to this invention is a metallurgical process that utilizes the following property: when a metallic material consisting of a chemical compound, an alloy, or a non-equilibrium alloy is immersed in a metal bath, the third component of the metallic material is selectively dissolved in the metal bath, depending on the heat of mixing with the component of the metal bath. This allows the remaining component to form a structure with fine interstices. Therefore, this manufacturing process for metallic materials according to this invention makes it possible to produce metallic materials with a pore size in the nanometer range by removing any material adhering to the formed, minute interstices. Such a material can also be easily produced with all base metals.Furthermore, this invention can also be applied to substances containing metal components such as tin, carbon, or metalloids like silicon, boron, or germanium. Moreover, the first, second, and third components need not necessarily be simple, pure elements, but can also consist of compound elements.

[0015] In the manufacturing process for metallic materials according to this invention, metallic materials are produced that consist of a chemical compound, an alloy, or a non-equilibrium alloy, which initially simultaneously contain a second component and a third component. Furthermore, the second and third components each have a positive and negative heat of mixing, respectively, and the first component is selected such that its melting point is lower than that of the metallic material or that of the second component. The metal bath is heated such that the temperature of the first component is above its melting point but lower than the minimum value of the liquidus curve temperature, within the composition variation range, until the second component is reached and the third component of the metallic material decreases.

[0016] The metallic material containing the second and third components is immersed in the metal bath, which consists of the first component. Because the third component in the metallic material has a positive heat of mixture with the first component, it dissolves in the metal bath. Simultaneously, because the second component has a negative heat of mixture with the first component, it remains on the surface of the metallic material without dissolving in the metal bath. As these second components combine with other similarly remaining components, particles on the nanometer scale are formed. Because these particles only bond at certain points, a structure with nanometer-scale gaps forms spontaneously.Furthermore, the size of the gaps produced and their gap rate can also be changed in this process by altering the temperature of the metal bath and the immersion time of the metallic material.

[0017] In the manufacturing process for metallic materials according to this invention, after the metallic material has been removed from the metal bath, adhering mixture deposits that are present on the surface or within the spaces between components and that contain the first or third component are selectively dissolved and removed by means of an acidic or alkaline aqueous solution. This results in a metallic material possessing extremely fine pores in the nanometer range, with the second component as its main component, and free of adhering mixture deposits. This is achieved by using an acidic or alkaline aqueous solution that selectively dissolves only the adhering mixture deposits without dissolving the second component. Otherwise, the adhering mixture deposits to be removed would be present, for example, on the outer surfaces of the manufactured metallic material or within the fine spaces between components, or they would fill these fine spaces.

[0018] In the manufacturing process for metallic materials according to this invention, the first component should preferably be Mg, Ca, Bi or rare earth metals or mixtures such as alloys or chemical compounds having one of these elements as a major component; the second component should be Ti, Zr, Nb, Ta, Cr, Mo, W, Fe or Sn or mixed solids such as alloys or chemical compounds having one or more of these elements as a major component; the third component should be Cu, Ni, Co, Fe or Ca or mixed solids such as alloys or chemical compounds having one or more of these elements as a major component.

[0019] In the manufacturing process for metallic materials according to this invention, a metallic material can also be produced that has a surface-treated layer with extremely fine pores by immersing the metallic material in the metal bath, whereby the third component is selectively dissolved from the surface layer of the metallic material. In this case, a metallic material can be produced that has pores in the nanometer range only in its surface-treated layer.

[0020] In the manufacturing process for metallic materials according to this invention, the third component can consist of nickel, and the metallic material can consist of a nickel-containing alloy. In this case, the nickel (Ni) dissolves in the metal bath, and a nickel-free metallic material can be produced in which the remaining second component is compacted and has fine pores. "Nickel-free" here means that the concentration of nickel atoms in the material is at most 1.0%. If nickel is only removed from the surface layer of the metallic material, a nickel alloy can be produced whose surface is nickel-free. In this case, fine pores are formed only on the nickel-free surface; the interior of the surface-treated layer retains the nickel-containing alloy with its excellent mechanical and functional properties.The resulting metallic material therefore retains its original mechanical properties and does not degrade overall. The leaching of nickel ions from the surface layer is suppressed, thus achieving excellent biocompatibility. The immersion time of the nickel-containing alloy in the metal bath must be carefully controlled so that the surface-treated layer only expands to the extent necessary to maintain the favorable mechanical properties of the material as a whole.

[0021] In the manufacturing process for metallic materials according to this invention, the metallic material can also be a nickel-containing alloy with Ti as the major component, stainless steel containing Ni, or nickel-containing alloys with Co or Cr as the major component. In these cases, the metallic material is, for example, Nitinol (a shape memory alloy of Ti and Ni), a nickel-containing stainless steel alloy containing austenitic stainless steel SUS316L, or nickel-containing cobalt-chromium alloys (Co-Cr) such as ASTM F90, F562, or F1058.

[0022] The metallic material according to this invention is characterized by the fact that it was produced using the manufacturing process for metallic materials according to this invention. The metallic material according to this invention possesses fine pores in the nanometer range. If this material consists of a nickel-containing alloy from which the nickel has been leached only from the surface layer of the metallic material, the mechanical properties of the material as a whole are retained, and because the leaching of nickel ions is suppressed, it possesses excellent biocompatibility. [Effect of the invention]

[0023] This invention provides a manufacturing process for easily making non-noble metallic materials porous with a pore size in the nanometer range, or for creating such a metallic material. Furthermore, it provides a manufacturing process and a metallic material in which the material as a whole does not lose its favorable mechanical properties and exhibits excellent biocompatibility, suppressing the release of nickel ions. [Simple explanations of the illustrations]

[0024] [ Fig. The manufacturing process for metallic materials according to the first application of this invention, wherein (a) is a side view showing the step when the metallic material is immersed in the molten metal bath; (b) is an enlarged side view of a part thereof; (c) is a side view of the metallic material removed from the molten metal bath; (d) is a side view showing the step when the metallic material is immersed in the acidic or alkaline aqueous solution; and (e) is a side view showing the produced metallic material.

[0025] [ Fig. ] A microscopic image of a porous titanium-zirconium metal produced using the manufacturing process for metallic materials according to the first application of this invention.

[0026] [ Fig. A graph showing the relationship between the atomic ratio of copper contained in the metallic material and the porosity of the produced metallic material – specifically, the porous titanium-zirconium metal. Fig. .

[0027] [ Fig. The manufacturing process for metallic materials according to the second application of this invention, wherein (a) is a side view showing the step when the metallic material is immersed in the molten metal bath; (b) is an enlarged side view of a part thereof; (c) is a side view of the metallic material removed from the molten metal bath; (d) is a side view showing the step when the metallic material is immersed in the acidic or alkaline aqueous solution; (e) is a side view showing the produced metallic material; and (f) is a side view showing an enlarged view of the area of ​​the produced metallic material in (e) marked by the dashed line.

[0028] [ Fig. ] A microscopic image of a cross-sectional surface of a nitinol wire whose surface is coated with a titanium layer and which was produced using the manufacturing process for metallic materials according to the second application of this invention.

[0029] [ Fig. A graph showing the relationship between the atomic ratio of ytterbium contained in the metal melt bath and the thickness of the tempered titanium surface; this is a nitinol metal whose surface was tempered with titanium and which was produced by the manufacturing process for metallic materials according to the second application of this invention, wherein a Mg-Yb alloy was used as a component for the metal melt bath. [Description of the application forms of this invention]

[0030] The following section explains application forms of this invention with reference to the illustrations. Fig. until Fig. This document describes the first application of the manufacturing process for metallic materials, or for such a metallic material. Here, one application of this invention will first be explained, using as an example a titanium material with fine pores; for this purpose, magnesium is used as the first component, titanium as the second, and copper as the third. According to Miedema's model, the heat of mixing occurring between magnesium and titanium, between titanium and copper, and between magnesium and copper is calculated to be 16 kJ / mol, 9 kJ / mol, and 3 kJ / mol, respectively (see Journal of the Japan Institute of Metals: 2005, Volume 46, page 2818).Magnesium and titanium repel each other due to their positive and negative signs, while titanium and copper, as well as magnesium and copper, have the property of forming mixtures that can take the form of a chemical compound or an alloy.

[0031] First, the metallic material 1 manufactured with the components titanium and copper. This is done, as in Fig. shown in the melting pot 2 into the molten metal bath 3 (Metal bath) immersed, which contains magnesium; the metal melting bath is adjusted so that the copper is dissolved in the metallic material. 1 The concentration decreases, but the temperature is lower than the minimum value of the liquidus curve temperature, within the composition variation range until the titanium component is reached. The copper component within the metallic material 1 then begins in the molten metal bath 3to dissolve, but the titanium component remains on the surface of the metallic material. 1 back; as the other remaining titanium components repeatedly bond with each other, particle-like structures form spontaneously. 4 of a size in the nanometer range, as in Fig. shown. These tiny particle-like structures. 4 They bond together in some places, forming gaps between them on the nanometer scale; these gaps are filled by magnesium components from which the copper has been dissolved.

[0032] The metallic material 1 , which has undergone the processing described above, is extracted from the molten metal bath 3 Removed and cooled to room temperature. As in Fig. shown, adhere to the part of the metallic material that is in the molten metal bath 3It had been submerged, and mixed deposits of copper and magnesium were found inside and around the circumference. When one considers this part of the metallic material... 1 , on which the mixed deposits 5 are – as in Fig. shown – in the container 6 immerses in which an acidic or alkaline aqueous solution 7 If so, then only the mixed deposits will be affected. 5 in acidic or alkaline aqueous solution 7 dissolved and removed. If it is then taken from the acidic or alkaline aqueous solution 7 If you take it out and let it air dry, you have – as in Fig. shown – the metallic material formed from titanium 8 The invention is produced and equipped with pores having a pore size in the nanometer range. The first application of this invention is explained below using a specific example. [Application form 1]

[0033] Approximately 30 g of Cu was melted in an atmosphere of pure argon gas using the arc melting process. 70 Ti 15 Zr 15 A pre-alloy with an atomic ratio of Cu:Ti:Zr of 70:15:15 was produced. This pre-alloy was mechanically crushed, and then approximately 5 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0034] Then 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 700°C at all times; thus the molten metal bath 3produced. At this temperature, the copper components in the Cu 70 Ti 15 Zr 15 reduced, but the temperature must be set so that it is lower than the 900°C of the minimum value of the liquidus curve temperature, within the composition variation range until the Ti 50 Zr 50 -component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about one second. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element copper has separated from the round, rod-shaped metallic material. 1 into the magnesium metal molten bath 3 dissolved; the remaining titanium and zirconium repeatedly bond together, forming alloy particles. 4with a particle size of approximately 500 nm; by bonding together at certain points, gaps are created which are filled with the adhering particles. 5 from the magnesium component – ​​into which the copper was also dissolved.

[0035] The part of the round rod-shaped metal material 1 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and copper had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0036] The result of this is in Fig. shown – it was made of Ti 50 Zr 50shaped metallic material 8 The material is manufactured and possesses fine pores with a pore size in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 40%; the specific surface area, defined as the ratio of titanium-zirconium surface area to titanium-zirconium volume, was determined to be approximately 2.4 × 10⁻⁶. 7 m 2 / m 3 calculated.

[0037] By examining the metallic material 1 By changing the atomic ratios of titanium, zirconium, and copper, one can determine the pore rate and the specific surface area of ​​the resulting porous metallic material. 8 made of titanium and zirconium. The relationship between the atomic ratio of copper in the metallic material. 1 and the porosity of the manufactured porous metallic material 8 titanium and zirconium are used in Fig. shown.

[0038] As in Fig. The porosity of the manufactured porous metallic material is shown. 8 the greater the higher the copper atom ratio, which is then in the magnesium metal melting bath 3 is extracted. [Application form 2]

[0039] Approximately 30 g of Cu was melted in an atmosphere of pure argon gas using the arc melting process. 50 Ti 30 AG 20 A pre-alloy with an atomic ratio of Cu:Ti:Ag of 50:30:20 was produced. This pre-alloy was mechanically crushed, and then approximately 5 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0040] Then 10 g of pure magnesium were placed in the crucible. 2A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 700°C at all times; thus the magnesium metal melt bath was formed. 3 produced. At this temperature, the copper components in the Cu 50 Ti 30 AG 20 The temperature is reduced, but it must be set below the 950°C minimum value of the liquidus curve temperature, within the composition variation range, until the titanium component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about one second. 3After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the elements copper and silver have leached out of the round, rod-shaped metallic material. 1 into the magnesium metal molten bath 3 dissolved; the remaining titanium repeatedly bonds together, forming tiny particles. 4 with a particle size of approximately 400 nm; by bonding together at certain points, gaps are created which are filled with the adhering particles. 5 from the magnesium component – ​​into which the copper and silver were also dissolved.

[0041] The magnesium metal melt bath 3 extracted and cooled metallic material 1 , was immersed in an aqueous solution of nitric acid for 30 minutes at room temperature 7 , which was adjusted to a concentration of 0.1 mol; after the mixed deposits consisting of magnesium, copper and silver had been removed5 Once dissolved and removed, it was extracted and dried in normal air.

[0042] The result was a metallic material formed from titanium. 8 The material is manufactured and possesses fine pores with a pore size in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 43%; the specific surface area, defined as the ratio of titanium surface area to titanium volume, was determined to be approximately 2.1 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 3]

[0043] Approximately 30 g of Cu was melted in an atmosphere of pure argon gas using the arc melting process. 70 Ti 30A pre-alloy with a Cu:Ti atomic ratio of 7:3 was produced. This pre-alloy was mechanically crushed, and then approximately 5 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0044] Then 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 700°C at all times; thus the magnesium metal melt bath was formed. 3 produced. At this temperature, the copper components in the Cu 70 Ti 30The temperature is reduced, but it must be set below the 868°C minimum value of the liquidus curve temperature, within the composition variation range, until the titanium component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about one second. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element copper has separated from the round, rod-shaped metallic material. 1 into the magnesium metal molten bath 3 dissolved; the remaining titanium repeatedly bonds together, forming tiny particles. 4 with a particle size of approximately 400 nm; by bonding together at certain points, gaps are created which are filled with the adhering particles. 5 from the magnesium component – ​​into which the copper was also dissolved.

[0045] The part of the round rod-shaped metal material 1 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and copper had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0046] The result was a metallic material formed from titanium. 8The material is manufactured and possesses fine pores with a pore size in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 47%; the specific surface area, defined as the ratio of titanium surface area to titanium volume, was determined to be approximately 2.4 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 4]

[0047] Approximately 30 g of Cr were melted in an atmosphere of pure argon gas using the arc melting process. 30 Co 70 A pre-alloy with a Cr:Co atomic ratio of 3:7 was produced. This pre-alloy was mechanically crushed, and then approximately 6 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0048] Then 15 g of pure cerium were placed in the melting crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 900°C at all times; thus the cerium metal melt bath was formed. 3 produced. At this temperature, the cobalt components in the Cr are converted into 30 Co 70 The temperature is reduced, but it must be set below the 1395°C minimum value of the liquidus curve temperature, within the composition variation range, until the chromium component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the cerium metal molten bath for about one second. 3After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element cobalt has leached out of the round, rod-shaped metallic material. 1 into the cerium metal melting bath 3 dissolved; the remaining chromium repeatedly recombines, forming tiny particles. 4 with a particle size of approximately 700 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5 from the cerium component – ​​into which the cobalt was also dissolved.

[0049] The part of the round rod-shaped metal material 1 , which comes from the cerium metal melting bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of cerium and cobalt had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0050] The result was a metallic material formed from chromium. 8 The material is manufactured with fine pores, measuring in the nanometer range. Analysis of a photograph of a cross-sectional area revealed a pore size of 35%; the specific surface area, defined as the ratio of chromium surface area to chromium volume, was determined to be approximately 2.0 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 5]

[0051] Approximately 30 g of Zr was melted in an atmosphere of pure argon gas using the arc melting method. 30 Cu 70A pre-alloy with a Zr:Cu atomic ratio of 3:7 was produced. This pre-alloy was mechanically crushed, and then approximately 5 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0052] Then 15 g of pure cerium were placed in the melting crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 830°C at all times; thus the cerium metal melt bath was formed. 3 produced. At this temperature, the copper components in the Zr 30 Cu 70The temperature is reduced, but it must be set so that it is lower than the 891°C minimum value of the liquidus curve temperature, within the composition variation range, until the zirconium component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the cerium metal molten bath for about one second. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element copper has separated from the round, rod-shaped metallic material. 1 into the cerium metal melting bath 3 dissolved; the remaining zirconium repeatedly bonds together, forming tiny particles. 4 with a particle size of approximately 600 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5from the cerium component – ​​into which the copper was also dissolved.

[0053] The part of the round rod-shaped metal material 1 , which comes from the cerium metal melting bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of cerium and copper had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0054] The result was a porous metallic material formed from zirconium. 8The material is manufactured and possesses fine pores with a pore size in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 36%; the specific surface area, defined as the ratio of zirconium surface area to zirconium volume, was determined to be approximately 2.0 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 6]

[0055] Approximately 30 g of Mo was melted in an atmosphere of pure argon gas using the arc melting method. 30 Ni 70 A pre-alloy with a Mo:Ni atomic ratio of 30:70 was produced. From this pre-alloy, the round-bar-shaped metallic material was cast in an atmosphere of pure argon gas using the copper casting process. 1 manufactured with a diameter of 1 mm and a length of approximately 50 mm.

[0056] Then 15 g of pure cerium were placed in the melting crucible. 2A graphite sample with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 1100°C at all times; thus the cerium metal melt bath was formed. 3 produced. At this temperature, the nickel components in the mo 30 Ni 70 The temperature is reduced, but it must be set so that it is lower than the 1312°C minimum value of the liquidus curve temperature, within the composition variation range until the molybdenum component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the cerium metal molten bath for about one second. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached out of the round, rod-shaped metallic material. 1into the cerium metal melting bath 3 dissolved; the remaining molybdenum repeatedly bonds with each other, forming tiny particles. 4 with a particle size of approximately 700 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5 from the cerium component – ​​into which the nickel was also dissolved.

[0057] The part of the round rod-shaped metal material 1 , which comes from the cerium metal melting bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of cerium and nickel had dissolved. 5Once dissolved and removed, it was extracted and dried in normal air.

[0058] The result was a metallic material formed from molybdenum. 8 The material produced has fine pores with a pore size in the nanometer range. Analysis of a photograph of a cut surface revealed a pore rate of 40%; the specific surface area, defined as the ratio of molybdenum surface area to molybdenum volume, was determined to be approximately 1.9 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 7]

[0059] Approximately 30 g of Ni was melted in an atmosphere of pure argon gas using the electron beam melting process. 70 W 30 It was produced with a W:Ni atomic ratio of 30:70. From this master alloy, the round-bar-shaped metallic material was produced in an atmosphere of pure argon gas using the arc casting process. 1manufactured with a diameter of 1.5 mm and a length of approximately 30 mm.

[0060] Then 15 g of pure cerium were placed in the melting crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 1600°C at all times; thus, the cerium metal melt bath was formed. 3 produced. At this temperature, the nickel components in the W 30 Ni 70 The temperature is reduced, but it must be set so that it is lower than the 1850°C minimum value of the liquidus curve temperature, within the composition variation range, until the tungsten component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the cerium metal molten bath for about one second. 3After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached out of the round, rod-shaped metallic material. 1 into the cerium metal melting bath 3 dissolved; the remaining tungsten repeatedly recombines, forming tiny particles. 4 with a particle size of approximately 700 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5 from the cerium component – ​​into which the nickel was also dissolved.

[0061] The part of the round rod-shaped metal material 1 , which comes from the cerium metal melting bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of cerium and nickel had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0062] The result was a porous metallic material formed from tungsten. 8 The material is manufactured and possesses fine pores with a pore size in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 30%; the specific surface area, defined as the ratio of tungsten surface area to tungsten volume, was determined to be approximately 2.1 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 8]

[0063] Approximately 30 g of Ta was melted in an atmosphere of pure argon gas using the electron beam melting process. 36 Ni 64A pre-alloy with a Ta:Ni atomic ratio of 36:64 was produced. This pre-alloy was mechanically crushed, and then approximately 7 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0064] Then 15 g of pure cerium were placed in the melting crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 900°C at all times; thus the cerium metal melt bath was formed. 3 produced. At this temperature, the nickel components in the Ta 36 Ni 64The temperature is reduced, but it must be set so that it is lower than the 1395°C minimum value of the liquidus curve temperature, within the composition variation range, until the tantalum component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the cerium metal molten bath for about one second. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached out of the round, rod-shaped metallic material. 1 into the cerium metal melting bath 3 dissolved; the remaining tantalum repeatedly recombines, forming tiny particles. 4 with a particle size of approximately 700 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5from the cerium component – ​​into which the nickel was also dissolved.

[0065] The part of the round rod-shaped metal material 1 , which comes from the cerium metal melting bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of cerium and nickel had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0066] The result was a porous metallic material formed from tantalum. 8The resulting material has fine pores with a pore size in the nanometer range. Analysis of a photograph of a cut surface revealed a pore rate of 29%; the specific surface area, defined as the ratio of tantalum surface area to tantalum volume, was determined to be approximately 1.8 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 9]

[0067] Approximately 30 g of Fe was melted in an atmosphere of pure argon gas using the arc melting process. 50 Ti 50 A pre-alloy with a Fe:Ti atomic ratio of 50:50 was produced. This pre-alloy was mechanically crushed, and then approximately 7 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0068] Then 15 g of pure samarium were placed in the melting pot. 2 A graphite sheet with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 1080°C at all times; thus the samarium metal melt bath was produced. 3 produced. At this temperature, the iron components in the Fe 50 Ti 50 The temperature is reduced, but it must be set below the 1085°C minimum value of the liquidus curve temperature, within the composition variation range, until the titanium component is reached. The round rod-shaped metallic material 1 is suspended by means of a molybdenum wire; after being immersed in the samarium metal molten bath for about one second 3After being immersed, it is removed into an argon gas atmosphere and cooled. During this time, the element iron has separated from the round, rod-shaped metallic material. 1 into the samarium metal melting bath 3 dissolved; the remaining titanium repeatedly bonds together, forming tiny particles. 4 with a particle size of approximately 400 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5 from the samarium component – ​​into which the iron was also dissolved.

[0069] The part of the round rod-shaped metal material 1 , which comes from the samarium metal melting bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of samarium and iron had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0070] The result was a porous metallic material formed from titanium. 8 The material is manufactured with fine pores, measuring in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 31%; the specific surface area, defined as the ratio of titanium surface area to titanium volume, was determined to be approximately 2.2 × 10⁻⁶. 7 m 2 / m 3 calculated. [Application form 10]

[0071] Approximately 30 g of Cu was melted in an atmosphere of pure argon gas using the arc melting process. 70 T 25,4 Zr 1,7 Cr 2,9A pre-alloy was produced that has an atomic ratio of Cu:Ti:Zr:Cr of 70:25.4:1.7:2.9. This pre-alloy was mechanically crushed, and then approximately 5 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0072] Then 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 800°C at all times; thus the magnesium metal melt bath was formed. 3 produced at this temperature. The copper component in the Cu 70 Ti 25,4 Zr 1,7 Cr 2,9reduced, but the temperature must be set so that it is lower than the 868°C of the minimum value of the liquidus curve temperature, within the composition variation range until the Ti 84,7 Zr 5,6 Cr 9,7 -component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about 60 seconds. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element copper has separated from the round, rod-shaped metallic material. 1 into the magnesium metal molten bath 3 dissolved; the remaining titanium, zirconium and chromium repeatedly bond together, forming tiny particles. 4 with a particle size of approximately 500 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5from the magnesium component – ​​into which the copper was also dissolved.

[0073] The part of the round rod-shaped metal material 1 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and copper had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0074] As a result, a product made of Ti was developed 84,7 Zr 5,6 Cr 9,7 shaped metallic material 8The material is manufactured and possesses fine pores with a pore size in the nanometer range. Structural analysis using X-ray diffraction (XRD) revealed the crystal structure of the porous, coated surface layer. 9 It has a body-centered cubic (bcc) structure. Analysis of a photograph of a cross-sectional surface revealed a porosity of 31%; the specific surface area, defined as the ratio of titanium-zirconium-chromium surface area to titanium-zirconium-chromium volume, was determined to be approximately 2.2 × 10 7 m 2 / m 3 calculated. [Application form 11]

[0075] Approximately 30 g of Ni was melted in an atmosphere of pure argon gas using the arc melting process. 70 Fe 23,4 Cr 6,6A pre-alloy was produced that has an atomic ratio of Ni:Fe:Cr of 70:23.4:6.6. This pre-alloy was mechanically crushed, and then approximately 5 g of it were inserted into a 70 mm long quartz die with an inner diameter of 7 mm, where, in an atmosphere of pure argon gas, the metallic material was cast using the copper casting process. 1 It was manufactured as a round rod with a diameter of 1 mm and a length of approximately 50 mm.

[0076] Then 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 900°C at all times; thus the magnesium metal melt bath was formed. 3 produced at this temperature. The nickel content in the Ni 70 Fe 23,4 Cr 6,6reduced, but the temperature must be set so that it is lower than the 1430°C of the minimum value of the liquidus curve temperature, within the composition variation range until the Fe 78 Cr 22 -component is reached. The round rod-shaped metallic material 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about 60 seconds. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached out of the round, rod-shaped metallic material. 1 into the magnesium metal molten bath 3 dissolved; the remaining iron and chromium repeatedly recombine, forming tiny particles. 4 with a particle size of approximately 800 nm; by these particles 4 Where they connect, gaps are created that are filled with the mixed substances. 5from the magnesium component – ​​into which the nickel was also dissolved.

[0077] The part of the round rod-shaped metal material 1 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and the mixture residues were removed. 5 has been placed in a beaker 6 given, in which an aqueous solution of nitric acid 7 was, which was adjusted to a concentration of 0.1 mol, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and nickel had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0078] As a result, a material made of Fe was produced 78 Cr 22 shaped metallic material 8The material is produced and possesses fine pores with a pore size in the nanometer range. Analysis of a photograph of a cross-sectional surface revealed a pore rate of 31%; the specific surface area, defined as the ratio of iron-chromium surface area to iron-chromium volume, was determined to be approximately 2.2 × 10⁻⁶. 7 m 2 / m 3 calculated.

[0079] The Fig. until Fig. This document describes the second application of the manufacturing process for metallic materials, or such a metallic material. Here, the second application of this invention will be explained, for which, as an example, a nitinol material is produced that has a tempered surface layer which – after the nickel has been dissolved from the surface layer – is formed by the remaining titanium with fine pores; the metallic material used is nitinol, a shape-memory nickel alloy of titanium and nickel (Ti-Ni) with a nickel atom content between 48.5 and 51.5%; for this purpose, cerium is used for the first component, titanium for the second component, and nickel for the third component.

[0080] When Nitinol is used, the heat of mixing between cerium and titanium, between titanium and nickel, and between cerium and nickel, respectively, is calculated according to Miedema's model to be +18 kJ / mol, -35 kJ / mol, and -28 kJ / mol (see Journal of the Japan Institute of Metals: 2005, Volume 46, pages 2818–2819). Cerium and titanium repel each other due to their positive and negative signs, while titanium and nickel, as well as cerium and nickel, have the property of forming mixtures that can take the form of a chemical compound or an alloy.

[0081] As in Fig. The metallic material consisting of nitinol is shown. 1 into the molten metal bath 3 (Metal bath) in the crucible 2The titanium is dipped, containing cerium; the cerium content is adjusted so that the nickel in the nitinol decreases, but the temperature remains below the minimum value of the liquidus curve temperature, within the composition variation range, until the titanium component is reached. The nickel component is located on the surface of the metallic material. 1 Then it begins in the molten metal bath 3 to dissolve, but the titanium component remains on the surface of the metallic material. 1 back; as the other remaining titanium components repeatedly bond with each other, particle-like structures form spontaneously. 4 of a size in the range between nanometers and micrometers, as in Fig. shown. These tiny particle-like structures. 4They connect to each other at certain points and form gaps between them with a size ranging from nanometers to micrometers; these gaps are filled with mixed deposits. 5 filled with cerium, into which the nickel has dissolved and mixed.

[0082] The metallic material 1 , which has undergone the processing described above, is extracted from the molten metal bath 3 Removed and cooled to room temperature. As in Fig. The areas that are immersed in the molten metal bath are shown. 3 were submerged and had mixed deposits on them 5 are – these adhere to the surface of the metallic material 1 to fill the gaps – as in Fig. shown, into a vessel 6 – a beaker – containing an acidic or alkaline aqueous solution 7 immersed; only the mixed residues are removed there. 5into the acidic or alkaline aqueous solution 7 dissolved and removed. Then it is extracted from the acidic or alkaline aqueous solution. 7 Removed and left to air dry; this allows – as in the Fig. and (f) shown – a nitinol metal 8 produce a surface coated with titanium 9 has a surface with fine pores, with a pore size in the range between nanometers and micrometers. A specific example of the second application of this invention is shown below. [Application form 12]

[0083] As a metallic material 1 A nitinol wire (a shape-memory nickel alloy of titanium and nickel (Ti-Ni) with a nickel content of 51%) with a diameter of 330 μm and a length of 50 mm was used. Then, approximately 50 g of cerium were placed in the crucible. 2A titanium tube with an inner diameter of 50 mm and a depth of 15 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 850°C at all times; thus the molten metal bath 3 produced. At this temperature, the nickel content in the nitinol is reduced, but the temperature must be set so that it is lower than the 942°C minimum value of the liquidus curve temperature, within the composition variation range until the titanium content is reached.

[0084] The metallic material 1 Nitinol wire is immersed in the molten metal bath for approximately 240 seconds. 3 It is immersed; afterwards, it is removed in an argon gas atmosphere and cooled. The element nickel is present on the surface of the metallic material. 1 During this time, a cerium metal molten bath was formed. 3dissolved; the remaining titanium repeatedly bonds together, forming titanium particles. 4 with a particle size of approximately 1 μm; as these bond together at certain points, gaps are created which are filled with the adhering particles. 5 from the cerium component – ​​into which the nickel was also dissolved.

[0085] The part with the mixed residues 5 , which comes from the cerium metal melting bath 3 was pulled out and cooled, and which is on the surface layer of the metallic material 1 the mixed residues 5 has been placed in a beaker 6 with a 30% aqueous solution of nitric acid 7 given, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of cerium and nickel components had disintegrated. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0086] As a result – as in Fig. shown – a nitinol wire 8 manufactured, which has a porous, titanium-coated surface layer 9 possesses; this layer has a thickness of 5 μm from the surface, and the spaces between it are approximately 1 μm in size. Elemental analysis using energy-dispersive X-ray spectroscopy (EDS) revealed that the tempered titanium surface contains 9 99 atomic parts of titanium were concentrated and the atomic part of nickel was reduced to 0.9%.

[0087] The thickness of the tempered titanium surface layer 9 The process, which is produced on the nitinol surface, can be controlled by adjusting the metal melt bath. 3An alloy is selected from ytterbium, which, like cerium, is a rare-earth metal, and from magnesium, whose nickel release rate is lower than that of ytterbium, by changing the atomic ratio of ytterbium. The relationship of the atomic ratio of ytterbium in the molten metal bath 3 to the thickness of the tempered titanium surface layer 9 will be in Fig. shown. This relationship only holds true if the temperature of the molten metal bath is 3 The temperature is 850°C and the immersion time is 240 seconds.

[0088] As in Fig. The tempered surface layer made of titanium is shown. 9 The thicker the thickness, the higher the atomic ratio of ytterbium in the molten metal bath. 3 is that – compared to magnesium – it has a higher nickel leaching rate. [Application form 13]

[0089] As a metallic material 1A SUS316L plate, 10 mm wide, 30 mm long, and 1 mm thick, was prepared. SUS316L is a steel grade typical of austenitic stainless steels, with excellent properties regarding corrosion resistance, magnetic properties, rollability, machinability, and weldability; it is particularly distinguished by its excellent resistance to pitting and grain boundary corrosion. Then, 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 800°C at all times; thus the molten metal bath 3produced. At this temperature, the nickel content in the SUS316L is reduced, but the temperature must be set so that it is lower than the approximately 1450°C minimum value of the liquidus curve temperature, within the composition variation range until the remaining components are reached – after nickel etc. has been dissolved from the SUS316L.

[0090] The metallic material consisting of the SUS316L plate 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about 60 seconds. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached from the surface layer of the metallic material. 1 into the magnesium metal molten bath 3dissolved; the remaining components repeatedly recombine, forming pit-shaped gaps approximately 3 μm in size; mixed deposits adhere to this surface. 5 which consist of magnesium components and the nickel dissolved in them.

[0091] The part with the mixed residues 5 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and which is on the surface layer of the metallic material 1 the mixed residues 5 has been placed in a beaker 6 with a 30% aqueous solution of nitric acid 7 given, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and nickel components had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0092] The result was a metallic material made of SUS316L.8 produced, which has a porous, coated surface layer 9 possesses; this layer has a thickness of 8 μm from the surface, and the spaces between it are approximately 3 μm in size. Elemental analysis using energy-dispersive X-ray spectroscopy (EDS) revealed that the coated surface layer contains 9 had reduced the nickel concentration to 0.8 atomic parts. [Application form 14]

[0093] As a metallic material 1An ASTM F90 plate, 10 mm wide, 30 mm long, and 1 mm thick, was prepared. The ASTM F90 alloy is a cobalt alloy, primarily composed of 19.0–21.0 parts by mass of chromium, 14.0–16.0 parts by mass of tungsten, 9.0–11.0 parts by mass of nickel, 0.05–0.15 parts by mass of carbon, 1.0–2.0 parts by mass of manganese, a maximum of 3 parts by mass of iron, and a maximum of 0.4 parts by mass of silicon; it is characterized by excellent formability and workability. Then, 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 950°C at all times; thus the molten metal bath 3At this temperature, the nickel content in the ASTM-F90 is reduced, but the temperature must be set so that it is lower than the approximately 1410°C minimum value of the liquidus curve temperature, within the composition variation range until the remaining components are reached – after nickel, etc., has been dissolved from the ASTM-F90.

[0094] The metallic material consisting of the ASTM F90 plate 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about 300 seconds. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached from the surface layer of the metallic material. 1 into the magnesium metal molten bath 3dissolved; the remaining nickel-free components repeatedly bond together, forming pit-shaped gaps approximately 1.5 μm in size, which define the coated surface layer 9 form; nickel alloy deposits adhere to this surface 5 which consist of magnesium components and the nickel dissolved in them.

[0095] The part with the mixed residues 5 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and which is on the surface layer of the metallic material 1 the mixed residues 5 has been placed in a beaker 6 with a 30% aqueous solution of hydrochloric acid 7 given, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and nickel components had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0096] The result was a nickel-free metallic material made from ASTM-F90. 8 produced, which has a porous, coated surface layer 9 possesses; this layer has a thickness of 3 μm from the surface, and the pitted spaces between them have a size of approximately 1.5 μm. Elemental analysis using energy-dispersive X-ray spectroscopy (EDS) revealed that the porous, coated surface layer contains 9 had reduced the nickel concentration to 0.7 atomic parts. [Application form 15]

[0097] As a metallic material 1An ASTM F562 plate, 10 mm wide, 30 mm long, and 1 mm thick, was prepared. ASTM F562 is a cobalt alloy that also contains 19.0–21.0 wt. chromium, 9.0–10.5 wt. molybdenum, 33.0–37.0 wt. nickel, a maximum of 0.025 wt. carbon, 0.15 wt. manganese, a maximum of 1.0 wt. iron, a maximum of 0.15 wt. silicon, and a maximum of 1.0 wt. titanium; it is characterized by excellent strength, rollability, and corrosion resistance. Then, 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 850°C at all times; thus the molten metal bath 3At this temperature, the nickel content in the ASTM-F562 is reduced, but the temperature must be set so that it is lower than the approximately 1440°C minimum value of the liquidus curve temperature, within the composition variation range until the remaining components are reached – after nickel, etc., has been dissolved from the ASTM-F562.

[0098] The metallic material consisting of the ASTM F562 plate 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about 300 seconds. 3 After being immersed, it is removed in an argon gas atmosphere and cooled. During this time, the element nickel has leached from the surface layer of the metallic material. 1 into the magnesium metal molten bath 3dissolved; the remaining nickel-free components repeatedly bond together, forming pit-shaped gaps approximately 3 μm in size, which define the coated surface layer 9 form; nickel alloy deposits adhere to this surface 5 which consist of magnesium components and the nickel dissolved in them.

[0099] The part with the mixed residues 5 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and which is on the surface layer of the metallic material 1 the mixed residues 5 has been placed in a beaker 6 with a 30% aqueous solution of hydrochloric acid 7 given, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and nickel components had disintegrated. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0100] The result was a nickel-free metallic material made from ASTM-F562. 8 produced, which has a porous, coated surface layer 9 possesses; this layer has a thickness of 5 μm from the surface, and the pitted spaces between them have a size of approximately 3 μm. Elemental analysis using energy-dispersive X-ray spectroscopy (EDS) revealed that the porous, coated surface layer contains 9 had reduced the nickel concentration to 0.9 atomic parts. [Application form 16]

[0101] As a metallic material 1An ASTM F1058 grade 1 plate, 10 mm wide, 30 mm long, and 1 mm thick, was prepared. The ASTM F1058 grade 1 alloy is an iron alloy that also contains 19.0–21.0 wt. chromium, 6.0–8.0 wt. molybdenum, 14.0–16.0 wt. nickel, a maximum of 0.025 wt. carbon, 1.5–2.5 wt. manganese, a maximum of 1.20 wt. silicon, a maximum of 0.1 wt. beryllium, and 39.0–41.0 wt. cobalt; it is characterized by excellent machinability. Then, 10 g of pure magnesium were placed in the crucible. 2 A graphite core with an inner diameter of 30 mm and a depth of 50 mm was used; this was then melted in an atmosphere of pure argon gas using high frequencies and regulated to maintain a liquid temperature of 900°C at all times; thus the molten metal bath 3produced. This temperature must be set to a temperature at which the nickel content in the ASTM-F1058-grade1 decreases and which is below 1460°C – this is the minimum value of the liquidus curve temperature, within the composition variation range until the remaining components are reached – after nickel etc. has been leached out of the ASTM-F1058-grade1.

[0102] The metallic material consisting of the ASTM F1058 grade 1 plate 1 It is suspended by means of a molybdenum wire; after being immersed in the magnesium metal molten bath for about 300 seconds. 3 After being immersed, it was removed in an argon gas atmosphere and cooled. During this time, the element nickel leached from the surface layer of the metallic material. 1 into the magnesium metal molten bath 3dissolved; the remaining nickel-free components repeatedly bond together, forming pit-shaped gaps approximately 3 μm in size, which define the coated surface layer 9 form; nickel alloy deposits adhere to this surface 5 which consist of magnesium components and the nickel dissolved in them.

[0103] The part with the mixed residues 5 , which comes from the magnesium metal molten bath 3 was pulled out and cooled, and which is on the surface layer of the metallic material 1 the mixed residues 5 has been placed in a beaker 6 with a 30% aqueous solution of hydrochloric acid 7 given, where it remained at room temperature for 30 minutes; after the mixed deposits consisting of magnesium and nickel components had dissolved. 5 Once dissolved and removed, it was extracted and dried in normal air.

[0104] The result was a nickel-free metallic material made from ASTM-F1058-grade 1. 8 produced, which has a porous, coated surface layer 9 possesses; this layer has a thickness of 5 μm from the surface, and the pitted spaces between them have a size of approximately 3 μm. Elemental analysis using energy-dispersive X-ray spectroscopy (EDS) revealed that the coated surface layer contains 9 had reduced the nickel concentration to 0.8 atomic parts. Reference symbol list 1. Metallic material 2 crucibles 3 Metal melting bath 4 particles 5 mixed adhesions 6 vessels 7 (Acidic or alkaline) aqueous solution 8. Metallic material 9 Coated surface layer QUOTES INCLUDED IN THE DESCRIPTION

[0105] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited non-patent literature

[0106] ASTM-F90, F562 or F1058

[0021] “The Japan Institute of Metals”: ​​2005, Volume 46, Page 2818

[0030] “The Japan Institute of Metals”: ​​2005, Volume 46, pages 2818–2819

[0080] ASTM F90 plate

[0093] ASTM F90 alloy

[0093] ASTM-F90

[0093] ASTM-F90

[0093] ASTM F90 plate

[0094] ASTM-F90

[0096] ASTM F562 plate

[0097] ASTM F562 alloy

[0097] ASTM-F562

[0097] ASTM-F562

[0097] ASTM-F562-Platte

[0098] ASTM-F562

[0100] ASTM-F1058-grade1-Platte

[0101] ASTM-F1058-grade1-Legierung

[0101] ASTM-F1058-grade1

[0101] ASTM-F1058-grade1

[0101] ASTM-F1058-grade1-Platte

[0102] ASTM-F1058-grade1

[0104]

Claims

[1] A manufacturing process for metallic materials, characterized in that a metallic material consisting of a chemical compound, an alloy, or a non-equilibrium alloy is immersed in a metal bath consisting of the first component; the metallic material contains the second and third components, which have positive and negative heats of mixture with respect to the first component, respectively; furthermore, their melting points are above the freezing point of the metal bath; the metal bath is controlled such that the third component decreases in the metallic material and that its temperature is lower than the minimum value of the liquidus curve temperature, within the composition variation range, until the second component is reached; thereby, the third component can be selectively dissolved in the metal bath, and a metallic material with very fine interstitial spaces is obtained. [2] A manufacturing process for metallic materials as described in claim 1, characterized in that – after [the metallic material] has been removed from the metal bath – only the mixture adhering to the first component and the third component and adhering to the circumference or to the fine interstices are selectively dissolved and removed by means of an acidic or alkaline aqueous solution. [3] A manufacturing process for metallic materials as described in claims 1 and 2, characterized in that the first component is Mg, Ca, Bi or rare earth metals or mixtures such as alloys or chemical compounds having one of these elements as a main component; For the second component, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe or Sn are used, or mixed solids such as alloys or chemical compounds that have one or more of these elements as their main component; For the third component, Cu, Ni, Co, Fe or Ca are used, or mixed solids such as alloys or chemical compounds that have one or more of these elements as their main component. [4] A manufacturing process for metallic materials as described in claims 1, 2 or 3, characterized in that a metallic material is obtained – having fine spaces on its tempered surface layer – by immersing the metallic material in a molten metal bath, where the third component can be selectively dissolved from the surface layer of the metallic material. [5] A manufacturing process for metallic materials as described in claims 1, 2, 3 or 4, characterized in that the third component consists of nickel and that the metallic material consists of a nickel-containing alloy. [6] A manufacturing process for metallic materials as described in claim 5, characterized in that the metallic material consists of an alloy containing Ni and having Ti as its main component, stainless steel containing Ni or an alloy having Co and Cr as its main component and containing Ni. [7] A metallic material produced by a manufacturing process for metallic materials, to which any one of claims 1 to 6 applies.

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