Preparation method and application of a multi-scale metal metamaterial

Abstract

The present application belongs to the technical field of multi-scale metal metamaterials, and particularly relates to a preparation method and application of a multi-scale metal metamaterial. The present application adopts a 3D printing method to prepare a 3D printing metal material by taking metal alloy powder as raw material; the 3D printing metal material has a micrometer array hole structure; the 3D printing metal material is soaked in a chemical corrosion solution for dealloying to obtain the multi-scale metal metamaterial. The present application prepares a large-size multi-scale metal metamaterial by a 3D printing + dealloying method, and the prepared multi-scale metal metamaterial retains the micrometer hole structure of 3D printing, so that the metal material with a micro-nanometer hole structure also has the advantage of large specific surface area, and has the characteristics of high drug loading when used as a drug-loaded medical device implant. Meanwhile, the preparation method provided by the present application is simple and easy to implement, low in cost, and suitable for industrial application.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of nano-porous metal materials, and particularly relates to a preparation method and application of a multi-scale metal metamaterial. BACKGROUND

[0002] Nano-porous metal materials are a kind of functional structural materials that develop rapidly today, and have the characteristics of metals and other nano materials, and show a wide potential application prospect in catalysis, filtration, water dissociation, sensors, chemical synthesis, hydrogen storage, automobile exhaust treatment, drug loading and release, electrochemical energy storage and conversion, etc.

[0003] Nano-porous metal structure is composed of metal skeleton and pores in nanometer scale, and has the basic metal properties of metal materials. Compared with dense bulk metal materials, nano-porous metal is a nano-structured macro material, and has a large number of interconnected nano-pores in the interior, and the micro size of the metal skeleton is in nanometer scale. These structural characteristics endow the structure with many characteristics, such as small specific gravity, large specific surface area, and saving of raw materials.

[0004] At present, the main method for preparing nano-porous metal materials is dealloying. The basic principle of dealloying for preparing nano-porous metal materials is to use the different chemical properties of different metals, selectively remove the more active metal component or multiple metal components in the alloy by chemical method, and the remaining metal components spontaneously form a three-dimensional double-continuous porous network structure through diffusion, aggregation and other ways at the reaction interface. Generally, an alloy block is obtained by high-temperature smelting, and then a corrosion liquid is used for dealloying.

[0005] However, if the size of the alloy block is large (such as the height direction is greater than 2 mm), dealloying cannot be effectively performed, so the dealloying method cannot process nano-porous metal materials with large sample size. The sample size of the nano-porous metal material prepared by the traditional dealloying method is generally less than 2 mm, which seriously limits its application in drug-loaded medical implant devices. SUMMARY

[0006] The purpose of the present application is to provide a preparation method and application of a multi-scale metal metamaterial. The nano-porous metal prepared by the present application has the characteristics of multi-scale pore structure, super large size and large specific surface area, and overcomes the processing bottleneck of small sample size of traditional multi-scale metal metamaterials.

[0007] In order to achieve the above purpose, the present application provides the following technical scheme:

[0008] The present application provides a preparation method of a multi-scale metal metamaterial, comprising the following steps:

[0009] A 3D printed metal material is prepared using metal alloy powder as raw material through a 3D printing method; the 3D printed metal material has a micron-scale array hole structure.

[0010] The 3D printed metal material is annealed to obtain an annealed metal material.

[0011] The annealed metal material is immersed in a chemical etching solution for dealloying to obtain the multi-scale metallic metamaterial.

[0012] Preferably, the annealing temperature is 800–900°C and the holding time is 30–60 min.

[0013] Preferably, the 3D printed metal material is composed of an array of unit cells, including square honeycomb unit cells, simple cubic unit cells, or helical icosahedral unit cells.

[0014] In the hexahedral structure of the square honeycomb unit cell, only one set of two pairs of corresponding surfaces have through-hole structures. When the square honeycomb unit cell array is arranged, the surfaces of two adjacent unit cells with through-holes are in contact with each other. The 3D printed metal material constructed by the square honeycomb unit cell has a square honeycomb structure.

[0015] The simple cubic unit cell has a hexahedral structure with three pairs of corresponding surfaces having through-hole structures; the 3D printed metal material constructed from the simple cubic unit cell has a simple cubic structure.

[0016] Preferably, the size of the square honeycomb unit cell is 1.2 mm. 3 The rod diameter is 0.58mm, the array pattern is a 4×4 two-dimensional structure, and the 3D printed metal material composed of square honeycomb unit cell array has a size of 4.2mm×4.2mm×9mm and a relative density of 80.0%.

[0017] The size of the simple cubic unit cell is 1.2 mm. 3 The rod diameter is 0.78mm, the array pattern is a 4×4×9 three-dimensional structure, and the 3D printed metal material composed of a simple cubic unit cell array has a size of 4.3mm×4.3mm×10.3mm and a relative density of 81.0%.

[0018] The size of the helical icosahedral unit cell is 4 mm. 3 The array is a 2×2×3 three-dimensional structure. The 3D printed metal material, composed of a spiral icosahedral unit cell array, has a size of 8mm×8mm×12mm and a relative density of 80.0%.

[0019] Preferably, the working parameters of the 3D printing include: laser diameter of 50-60 mu m, laser power of 80-100 W, scanning speed of 600-800 mm / s, path spacing of 100-110 mu m, and layer thickness of 20-30 mu m; and the temperature of the metal alloy powder during the 3D printing is 80-100 DEG C.

[0020] Preferably, the Dv50 of the metal alloy powder is 40-45 mu m, the metal alloy powder is a CuMn alloy, and the CuMn alloy comprises metal elements with mass content of 44% Cu and 56% Mn.

[0021] Preferably, the chemical corrosion solution is a sulfuric acid solution, and the molar concentration of the sulfuric acid solution is 0.2-0.3 mol / L.

[0022] The temperature of the dealloying is 20-30 DEG C, and the time is greater than or equal to 5 days; and the chemical corrosion solution used for dealloying is replaced every 3 hours during the dealloying process.

[0023] The application provides a multi-scale metal metamaterial prepared by the preparation method.

[0024] Preferably, the smallest size in the three-dimensional size of the multi-scale metal metamaterial is greater than 2 mm.

[0025] The application provides an application of the multi-scale metal metamaterial in preparing a drug-loaded medical device implant.

[0026] The application firstly adopts a 3D printing method to obtain a 3D printed metal material with a micrometer array hole structure, and then through annealing treatment, the metal element composition distribution of the 3D printed metal material is more uniform, which is beneficial to obtaining a porous metal material with uniform nanopore distribution through dealloying, and in the dealloying process, the chemical corrosion solution can enter the hole structure of the 3D printed metal material and fully contact the inner surface of the 3D printed metal material, so that the 3D printed metal material can be chemically corroded more fully and efficiently. Therefore, the preparation method provided by the application can prepare a large-size multi-scale metal super material through the dealloying method, and the prepared multi-scale metal super material retains the micrometer hole structure of 3D printing, so that the metal material with micro-nanopore structure also has the advantage of large specific surface area, and has the characteristics of high drug loading when used as a drug-loaded medical device implant. In summary, the preparation method provided by the application is simple and easy to operate, low in cost, and the obtained nanoporous metal has the characteristics of multi-scale pore structure, super large size and large specific surface area, overcomes the processing bottleneck of small sample size of traditional multi-scale metal super materials, and is suitable for industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 Flow chart for preparing multi-scale metal super material for example;

[0028] Figure 2 Morphology diagram of multi-scale metal super material in example 1;

[0029] Figure 3 Actual object diagram of multi-scale metal super material prepared in examples 1-3;

[0030] Figure 4 Actual object diagram of multi-scale metal super material (fusor) prepared in example 4;

[0031] Figure 5 Microscopic characterization diagram of multi-scale metal super material in example 4;

[0032] Figure 6 CAD model diagram, CT characterization diagram and SEM characterization diagram of multi-scale metal super material prepared in examples 1-3;

[0033] Figure 7 Surface area diagram of multi-scale metal super material prepared in example 4 measured by mercury injection method;

[0034] Figure 8 Drug loading performance diagram of multi-scale metal super material prepared in example 4 evaluated by infrared spectrometer;

[0035] Figure 9 Metallographic composition diagram of 3D printed metal material before and after annealing treatment in example 4;

[0036] Figure 10 SEM photos and particle size distribution charts of CuMn alloys used for examples. DETAILED DESCRIPTION

[0037] The application provides a preparation method of a multi-scale metal metamaterial, comprising the following steps:

[0038] The 3D printing metal material is prepared by using a 3D printing method and taking metal alloy powder as raw material; the 3D printing metal material has a micrometer array hole structure.

[0039] The 3D printing metal material is subjected to annealing treatment to obtain an annealing treatment metal material.

[0040] The annealing treatment metal material is immersed in a chemical corrosion solution to perform dealloying, so as to obtain the multi-scale metal metamaterial.

[0041] In the application, all the preparation raw materials / components are commercially available products known by those skilled in the art, unless otherwise specified.

[0042] The 3D printing metal material is prepared by using a 3D printing method and taking metal alloy powder as raw material; the 3D printing metal material has a micrometer array hole structure.

[0043] In the application, before the 3D printing, the application preferably uses software to design a printing model of the 3D printing metal material. In the application, the software preferably comprises CAD or SOLIDWORKS. The application does not have special requirements for the specific design method of the printing model.

[0044] In the application, the 3D printing metal material has a topological structure. The 3D printing metal material is preferably composed of array-arranged unit cells, and the unit cell preferably comprises a square honeycomb unit cell, a simple cubic unit cell or a gyroid unit cell. Only one set of two corresponding surfaces of the hexahedral structure of the square honeycomb unit cell has a through-hole structure, and the surfaces with through-holes of adjacent two unit cells are in contact when the square honeycomb unit cells are array-arranged; the square honeycomb unit cell is a first cubic unit cell, and the 3D printing metal material constructed by the square honeycomb unit cell is a square honeycomb structure. Three sets of two corresponding surfaces of the hexahedral structure of the simple cubic unit cell have a through-hole structure; the 3D printing metal material constructed by the simple cubic unit cell is a cubic structure.

[0045] In the application, the 3D printing metal material of the gyroid unit cell member is a gyroid structure.

[0046] In the present application, the size of the square honeycomb cell is 1.2mm 3 , the rod diameter is 0.58mm, the array mode is a 4x4 two-dimensional structure, the size of the 3D printed metal material composed of the array of square honeycomb cells is 4.2mmx4.2mmx9mm, and the relative density is 80.0%. The size of the simple cubic cell is 1.2mm 3 , the rod diameter is 0.78mm, the array mode is a 4x4x9 three-dimensional structure, and the 4x4x9 three-dimensional structure refers to the array of 4x4 in the X and Y directions and the array of 9 in the Z direction. The size of the 3D printed metal material composed of the array of simple cubic cells is 4.3mmx4.3mmx10.3mm, and the relative density is 81.0%. The size of the gyroid cell is 4mm 3 , the array mode is a 2x2x3 three-dimensional structure, and the 2x2x3 three-dimensional structure refers to the array of 2x2 in the X and Y directions and the array of 3 in the Z direction. The size of the 3D printed metal material composed of the array of gyroid cells is 8mmx8mmx12mm, and the relative density is 80.0%.

[0047] In the present application, when the printing model of the 3D printed metal material is designed by software, the relative density (pRD) of the 3D printed metal material = V Solid / V Lattice , wherein V Solid is the volume of the solid part of the 3D printed metal material, and V Lattice is the volume occupied by the 3D printed metal material in three-dimensional space. V Solid and V Lattice are obtained in the printing model established by software. In a specific embodiment of the present application, the gyroid is a three-dimensional periodic minimal surface structure, and the gyroid cell is preferably constructed by a parametric equation in the K3Dsurf software, which is shown as formula 1:

[0048] f(x,y,z) = cos(0.25 x pi x x) x sin(0.25 x pi x y) + cos(0.25 x pi x y x sin(0.25 x pi x z) + cos(0.25 x pi x z) x sin(0.25 x pi x x) + t formula 1.

[0049] In the parametric equation shown in formula 1, one determined relative density Gyroid cell has two different values of t. In the present application, two t values of the determined relative density Gyroid cell are obtained according to the parametric equation shown in formula 1, the obtained two stl models are imported into UG (Siemens software), and a cuboid is cut through Boolean operation to obtain the Gyroid cell under the condition of determining the relative density. In the specific embodiment of the present application, the Gyroid cell with a relative density of 23.8% corresponds to t in the parametric equation shown in formula 1, and t is respectively t = 0 and t = -0.8. The Gyroid cell with a relative density of 80.0% corresponds to t in the parametric equation shown in formula 1, and t is respectively t = +0.9 and t = -0.9.

[0050] In the present application, the density of the 3D printed metal material is preferably ≥80%.

[0051] In the present application, the Dv50 of the metal alloy powder is 40-45 μm, and in the specific embodiment of the present application, the Dv10 of the metal alloy powder is 31.92 μm, the Dv50 is 42.74 μm, and the Dv90 is 89.09 μm. The metal alloy powder used in the present application has a particle size Dv50 of 40-45 μm and good sphericity. The metal alloy powder is a CuMn alloy, and the CuMn alloy comprises the following mass content of metal elements: 44% Cu and 56% Mn. In the present application, the device used for 3D printing is preferably TruPrint 1000 (TRUMPF Laser-und Systemtechnik GmbH). The working parameters of the 3D printing preferably include: the laser diameter is preferably 50-60 μm, more preferably 55 μm; the laser power is preferably 80-100 W, more preferably 90 W; the scanning speed is preferably 600-800 mm / s, more preferably 700 mm / s; the path spacing is preferably 100-110 μm, more preferably 105 μm; the layer thickness is preferably 20-30 μm, more preferably 25; the scanning strategy is preferably 67° rotation. The base material is preferably stainless steel. The disc diameter is preferably 0.15 mm, and the powder beam size is preferably: diameter 100 mm, height 100 mm. The 3D printing is carried out in a protective gas atmosphere, and the oxygen content of the protective gas is <100 ppm. The temperature of the metal alloy powder during 3D printing is preferably 80-100°C, more preferably 100°C. After the 3D printing is completed, the 3D printed metal material is manually removed from the 3D printing device by using wire cutting in the present application. A 0.3 mm plate structure is added at the bottom of the grid to compensate for the material removal of the wire cutting.

[0052] After obtaining the 3D printing metal material, the 3D printing metal material is annealed to obtain an annealed metal material. The annealing is preferably carried out in a quartz tube. The annealing temperature is preferably 800-900 DEG C, more preferably 850 DEG C; the holding time is preferably 30-60 min. The annealing is preferably carried out in a protective gas atmosphere, and the protective gas is preferably an inert gas, and is preferably argon. The present application preferably makes the metal element composition distribution of the 3D printing metal material more uniform through annealing, which is beneficial to obtaining a porous metal material with uniform nanopore distribution through dealloying.

[0053] After the annealing, the annealed metal material is immersed in a chemical etching solution for dealloying to obtain the multiscale metal metamaterial.

[0054] In the present application, the chemical etching solution is preferably a sulfuric acid solution, and the molar concentration of the sulfuric acid solution is preferably 0.2-0.3 mol / L, more preferably 0.25 mol / L. In a specific embodiment of the present application, the chemical etching solution is preferably purchased from Kowa Co., Ltd. The dealloying temperature is preferably 20-30 DEG C, and the time is preferably ≥5 days; preferably, the chemical etching solution used in the dealloying process is replaced every 3 hours. The total chemical etching solution used in the dealloying process is preferably replaced once.

[0055] In the present application, after the dealloying, the obtained metal sample is preferably washed, and the washing is preferably rinsing and soaking. The solvent used in the washing is preferably ethanol.

[0056] The present application provides a multiscale metal metamaterial obtained by the preparation method described in the above technical solution, wherein the multiscale metal metamaterial has a hierarchical pore structure, the hierarchical pore structure comprises a micropore structure and a nanopore structure, and the micropore structure is arranged in an array.

[0057] In the present application, the smallest dimension in the three-dimensional size of the multiscale metal metamaterial is preferably >2 mm, more preferably 4 mm.

[0058] In a specific embodiment of the present application, a specific example of the multiscale metal metamaterial is Figure 4 The fusion cage has a size of 40 mm x 29 mm x 18 mm.

[0059] The present application provides an application of the multiscale metal metamaterial described in the above technical solution in preparing a drug-loaded medical device implant.

[0060] The multiscale metal metamaterial provided by the present application has a hierarchical pore topology structure, and the maximum surface area is 22 m2 / g (meaning 1 kg of this material has a surface area equivalent to 3 football fields), which has good prospects for drug loading.

[0061] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0062] The following embodiments are all in accordance with Figure 1 The process for preparing multi-scale metallic metamaterials is shown.

[0063] Example 1

[0064] (1) Using Solidwork software, 3D printed metal materials were designed to form a square honeycomb structure from a square honeycomb unit cell array. Figure 6 The corresponding Square honeycomb printing model is designed with the relative density (ρRD) of the 3D printed metal material for the square honeycomb structure as V. Solid / V Lattice V Solid V is the volume of the solid part of the 3D printed metal material. Lattice It refers to the volume occupied by 3D-printed metal materials in three-dimensional space. V Solid and V Lattice The topological parameters of the 3D printed metal material for the Square honeycomb structure in this embodiment are obtained using the printing model built with Solidworks software. Table 1 shows the parameters of the 3D printed metal material for the Square honeycomb structure in this embodiment.

[0065] Table 1 Topology parameters for metallic metamaterial designs in Examples 1-3

[0066]

[0067] (2) 3D printing was performed using a TruPrint 1000 (TRUMPF Laser- und Systemtechnik GmbH) machine, and the metal powder raw material used was CuMn alloy powder. Figure 10The SEM photo and particle size distribution chart of the CuMn alloy powder used in Examples 1-4, the Dv10 of the CuMn alloy powder is 31.92 pm, the Dv50 is 42.74 pm, the Dv90 is 89.09 pm, and it has good sphericity. The CuMn alloy powder includes the following mass content of metal elements: 44% Cu and 56% Mn. The working parameters for 3D printing are shown in Table 2, and the alloy powder is preheated to a temperature of 100°C. After the manufacturing is completed, the obtained 3D printed metal material part is cooled to room temperature (25°C) in the machine. Then the component is manually removed from the build plate using wire cutting. A 0.3 mm plate is added at the bottom of the grid to compensate for the material removal of wire cutting.

[0068] Table 2 3D printing working parameters of Examples 1-4

[0069]

[0070] (3) The obtained 3D printed metal material is sealed in a quartz tube with an argon atmosphere, and then heated to 850°C for 30 min for homogenization annealing treatment.

[0071] (4) After annealing treatment, the 3D printed metal material after annealing treatment is dealloyed using an H2SO4 solution (0.25 mol / L) (Kehua Co., Ltd.) at room temperature (25°C). The sample dealloying time is 5 days, the H2SO4 solution is updated every 3 hours, and the total H2SO4 solution used for dealloying is also updated once during the dealloying process. Then the residual H2SO4 solution in the multi-scale metal metamaterial (NPM) hole structure obtained by dealloying is carefully cleaned by rinsing and soaking in ethanol.

[0072] Figure 2 The morphology chart of the multi-scale metal metamaterial in Example 1. From Figure 2 It can be seen that the multi-scale metal metamaterial prepared in Example 1 has a hierarchical pore structure, and Example 1 obtains a 3D printed metal material with a microporous honeycomb structure (Square honeycomb) by 3D printing, and then obtains a metal material with a nanoporous structure by dealloying.

[0073] Example 2

[0074] (1) The printing model of the 3D printed metal material of the simple cubic structure (Cubic) formed by the simple cubic unit array is designed by using the Solidwork software Figure 6 corresponding to Cubic in Solid Lattice , wherein V Solid ​V is the volume of all struts of the 3D-printed metallic material Lattice V is the external volume of the 3D-printed metallic material. Solid V is the volume of all struts of the 3D-printed metallic material Lattice are obtained in the printing model established using the Solidwork software. Table 1 gives the topological parameters of the 3D-printed metallic material with the Cubic structure in this embodiment.

[0075] Steps (2)-(4) are the same as in Embodiment 1, and a multi-scale metallic metamaterial is obtained.

[0076] Embodiment 3

[0077] (1) The printing model of the 3D-printed metallic material with the Gyroid structure formed by the array of gyroidal 24-cell unit cells is designed using the Solidwork software (Gyroid in FIG. 1). Figure 6 The relative density (pRD) of the 3D-printed metallic material with the Gyroid structure is designed to be V Solid / V Lattice , wherein V Solid is the volume of all struts of the 3D-printed metallic material, V Lattice is the external volume of the 3D-printed metallic material. Solid V is the volume of all struts of the 3D-printed metallic material Lattice are obtained in the printing model established using the Solidwork software. Table 1 gives the topological parameters of the 3D-printed metallic material with the Gyroid structure in this embodiment.

[0078] In this embodiment, the printing model of the 3D-printed metallic material is designed using the software, and the relative density (pRD) of the 3D-printed metallic material is V Solid / V Lattice , wherein V Solid is the volume of all struts of the 3D-printed metallic material, V Lattice is the external volume of the lattice. Solid V is the volume of all struts of the 3D-printed metallic material Lattice are obtained in the printing model established using the software. The gyroidal 24-cell is preferably constructed by the parameter equation shown in Formula 1 in the K3Dsurf software, and the relative density of the 3D-printed metallic material with the Gyroid structure is determined to be 80.0%, so that t in the parameter equation shown in Formula 1 is t = +0.9 and t = -0.9, respectively. The obtained two stl models are imported into UG (Siemens software), and the gyroidal 24-cell with the determined relative density is obtained by cutting the cuboid through Boolean operation. Table 1 gives the topological parameters of the 3D-printed metallic material with the Gyroid structure in this embodiment.

[0079] Steps (2)-(4) are the same as in Embodiment 1, and a multi-scale metallic metamaterial is obtained.

[0080] Figure 3 Images of the multi-scale metallic metamaterials prepared in Examples 1-3 are shown. Figure 6 CAD model diagrams, CT characterization diagrams, and SEM characterization diagrams of the multiscale metallic metamaterials prepared in Examples 1-3 are shown.

[0081] The density of NPM can be determined by ρ RD =m Beform / m After The calculation assumes that the sample volume does not change during dealloying, where m Beform and m After It refers to the quality of the samples before and after dealloying.

[0082] Table 3. Relative densities of dealloyed topologies prepared in Examples 1-3

[0083]

[0084] Example 4

[0085] (1) Designed using Solidwork software by Figure 4 The printed model of the fusion body shown is designed with the relative density (ρRD) of the supermetallic material of the fusion body structure as shown in the figure being V. Solid / V Lattice V Solid For the volume of all pillars of 3D printed metal material, V Lattice It is the external volume of the crystal lattice. V Solid and V Lattice The 3D printed metal material was obtained using a printing model created with Solidworks software. In this embodiment, the invention uses software to design the internal porous structure of the printed model to have a wall thickness of 0.8 mm and a pore diameter of 1.2 mm.

[0086] Steps (2) to (4) are the same as in Example 1, and multi-scale metallic metamaterials are obtained.

[0087] Figure 4 This is a photograph of the multi-scale metallic metamaterial (fusion device) prepared in Example 4; the dimensions of the fusion device prepared in Example 4 are: 40×29×18mm. 3 . Figure 5 These are microscopic characterization images of the multiscale metallic metamaterials in Example 4; (The remaining text appears to be a fragment and requires further context for accurate translation.) Figure 5 It can be seen that: Example 4 uses Mn-Cu alloy as raw material. After dealloying, only Cu element is left and Mn is basically removed. The resulting nanoporous structure has a rod diameter of 77.4 nm. Figure 7 This is a surface area map of the multi-scale metallic metamaterial prepared in Example 4, measured using the mercury vapor deposition method; (The remaining text appears to be a fragment and requires further context for accurate translation.) Figure 7It can be seen that the surface area of the fusion device prepared in Example 4 is 22m 2 / g, i.e. 1 Kg of the material, the surface of which is as large as three football fields, has good drug loading prospects. Figure 8 Fig. 4 is a graph for evaluating the drug loading performance of the multi-scale metal metamaterial prepared in Example 4 by using an infrared spectrometer; and Figure 8 It can be seen that the characteristic absorption peak of the nano-carrier prepared in Example 4 is analyzed by using an American Nicolet AVATAR 360 infrared spectrometer (FT-IR), and the resolution of the infrared spectrum is 4cm -1 , and the recording range is from 400cm -1 to 4000cm -1 . It is shown that the fusion device prepared in Example 4 is a multi-scale, large-surface-area nano-porous material, which can successfully load drugs. Figure 9 Fig. 5 is a metallographic composition diagram of the 3D printing metal material before and after the annealing treatment in Example 4. It can be seen that Figure 9 Through the annealing treatment, the Cu element and the Mn element in the 3D printing metal material in Example 4 are obviously homogenized in the metallographic structure, which is beneficial to the de-alloying to obtain the fusion device product with uniform nano-pores.

[0088] The test results of Examples 1-3 are basically the same as those of Example 4.

[0089] Although the above examples have made a detailed description of the present application, it is only a part of the embodiments of the present application, but not all the embodiments, and other embodiments can be obtained according to the present embodiments without creativity, which all belong to the protection scope of the present application.

Claims

1. Use of a multiscale metallic metamaterial in the preparation of a drug-loaded medical device implant, characterized in that, The preparation method of the multiscale metal metamaterial comprises the following steps: The 3D printing metal material is prepared by using a 3D printing method and taking a metal alloy powder as a raw material, the metal alloy powder is a CuMn alloy, the CuMn alloy comprises metal elements with the following mass contents: 44% Cu and 56% Mn, the 3D printing metal material has a micrometer array hole structure, the 3D printing metal material is composed of array-arranged unit cells, the unit cells include square honeycomb unit cells, simple cubic unit cells or helical icosahedral unit cells; Only one set of two corresponding surfaces of the hexahedral structure of the square honeycomb unit cell has a through hole structure, when the square honeycomb unit cells are array-arranged, the surfaces with through holes of two adjacent unit cells are in contact with each other, the 3D printing metal material constructed by the square honeycomb unit cells has a square honeycomb structure; Three sets of two corresponding surfaces of the hexahedral structure of the simple cubic unit cell have through hole structures, the 3D printing metal material constructed by the simple cubic unit cells has a simple cubic structure; The 3D printing metal material is subjected to annealing treatment to obtain an annealing-treated metal material; The annealing-treated metal material is immersed in a chemical corrosion solution to perform dealloying, thereby obtaining the multiscale metal metamaterial, the chemical corrosion solution is a sulfuric acid solution, the molar concentration of the sulfuric acid solution is 0.2-0.3 mol / L, the dealloying temperature is 20-30 DEG C, and the time is greater than or equal to 5 days, the chemical corrosion solution is replaced every 3 hours during the dealloying process.

2. Use according to claim 1, characterized in that, The annealing treatment temperature is 800-900 DEG C, and the holding time is 30-60 min.

3. Use according to claim 1, characterized in that, The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honeycomb cell is 1.2mm 3 The size of the square honey The simple cubic unit cell has a size of 1.2 mm 3 The simple cubic unit cell has a size of 1.2 mm The size of the gyroidal icosahedral cell is 4mm 3 The array mode is 2x2x3 three-dimensional structure, the size of the 3D printing metal material composed of gyroidal icosahedral cell array is 8mmx8mmx12mm, and the relative density is 80.0%.

4. Use according to claim 1, characterized in that, The working parameters of the 3D printing include: a laser diameter of 50-60 μm, a laser power of 80-100 W, a scanning speed of 600-800 mm / s, an interpass distance of 100-110 μm, and a layer thickness of 20-30 μm, and the temperature of the metal alloy powder during the 3D printing is 80-100 DEG C.

5. Use according to claim 1 or 4, characterized in that, The Dv50 of the metal alloy powder is 40-45 μm.

6. Use according to claim 1, characterized in that, The multiscale metal metamaterial has a multistage pore structure, the multistage pore structure comprises a micropore structure and a nanopore structure, and the micropore structure is array-arranged.

7. Use according to claim 6, characterized in that, The smallest dimension in the three-dimensional size of the multiscale metal metamaterial is greater than 2 mm.

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