CN111137848A - Lightweight high-toughness multi-cell metal micro-nano structure and preparation method thereof - Google Patents
Lightweight high-toughness multi-cell metal micro-nano structure and preparation method thereof Download PDFInfo
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- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00214—Processes for the simultaneaous manufacturing of a network or an array of similar microstructural devices
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- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B81C2201/0156—Lithographic techniques
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Abstract
The invention provides a light high-toughness multi-cell metal micro-nano structure and a preparation method thereof, wherein the preparation method comprises the following steps: establishing a three-dimensional model of a three-dimensional multi-cell micro-nano structure; preparing a two-photon polymerized photosensitive resin; selecting a laser processing system; setting two-photon polymerization process parameters; laser is incident into the photosensitive resin by utilizing the laser processing system, and two-photon polymerization is carried out to obtain a three-dimensional multi-cell polymer micro-nano structure; and depositing a plurality of layers of metal on the surface of the polymer forming the three-dimensional multi-cell polymer micro-nano structure by adopting a physical deposition method, a chemical deposition method or a physical and chemical combined deposition method to prepare the high-toughness multi-cell metal micro-nano structure. The multi-cell metal micro-nano structure prepared by the invention integrates the geometric structure enhancement effect and the synergistic enhancement effect of the inherent properties of the multi-layer multi-performance material, and has the advantages of good toughness, light weight, simple process and easy operation. Therefore, the light high-strength multi-cell metal micro-nano structure can be prepared by the method.
Description
Technical Field
The invention relates to the technical field of micro-nano manufacturing, in particular to a lightweight high-toughness multi-cell metal micro-nano structure and a preparation method thereof.
Background
In the past, the improvement of material performance mainly depends on the change of the composition and the optimization of microstructure. In recent years, the advanced technology is utilized to prepare the three-dimensional micro-nano structure material with the performances of high strength, ultralow density and the like, which receives wide attention. The three-dimensional micro-nano structure is generally formed by materials which are connected with each other in a micro/nano size, and the materials have unique characteristics by combining the geometrical structure and the inherent characteristics of the material components, so that the three-dimensional micro-nano structure has wide engineering application potential in the fields of electronic devices, energy storage, biomedicine and the like.
Two-photon polymerization (TPP) technology is generated along with the development of Two-photon technology, and Two photons have the advantages of strong penetrating power and high spatial resolution, have wide application prospect in the fields of three-dimensional ultra-fine micromachining, three-dimensional high-density optical storage and the like, and greatly promote the preparation development process of micro-nano materials. The two-photon absorption has the two characteristics of good penetrability to materials and high space selectivity, and provides a foundation for realizing two-photon polymerization; in contrast to conventional photopolymerization, two-photon polymerization is a polymerization reaction initiated by a light-absorbing substance (monomer, initiator or photosensitizer) through two-photon absorption to generate a reactive group (radical or cation). The two-photon polymerization technology breaks through the optical diffraction limit, has nanometer processing resolution and can manufacture three-dimensional micro-nano structures in any shapes. Therefore, the two-photon polymerization-based 3D femtosecond laser direct writing technology enables the preparation of a high-quality high-precision multi-cell micro-nano structure to be possible, and is used for the rapid forming and preparation of the micro-nano structure of the key structural member. However, in the femtosecond laser direct writing process, the multi-cell micro-nano structure is mainly prepared by laser-induced polymer colloid reaction, and the components of the multi-cell micro-nano structure are organic polymer materials, although the multi-cell micro-nano structure has good elasticity, the strength is poor, so that the application of the multi-cell micro-nano structure is limited. Therefore, the development of a light-weight, high-toughness three-dimensional micro-nano structure is still an important challenge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a light high-strength and high-toughness multi-cell metal micro-nano structure and a preparation method thereof.
The technical scheme for solving the problems is as follows: a preparation method of a light high-strength and high-toughness multi-cell metal micro-nano structure is based on a composite gradient structure design, a composite manufacturing technology combining two-photon polymerization and a deposition process is adopted to manufacture the three-dimensional multi-cell micro-nano structure, a multi-layer metal material is deposited on the surface of a high polymer forming the three-dimensional micro-nano structure to form a composite metal layer with gradient change of mechanical properties, the strength and toughness of the polymer multi-cell micro-nano structure are improved, and therefore the light high-strength and high-toughness multi-cell metal micro-nano structure is prepared, and the preparation method comprises the following steps:
establishing a micro-nano structure three-dimensional model: establishing a three-dimensional model of a three-dimensional multi-cell micro-nano structure, and performing discrete layering;
preparing photosensitive resin: preparing a two-photon polymerized photosensitive resin;
selection of laser processing system: selecting a laser processing system;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing the laser processing system to enable laser to be incident into the photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, dissolving the non-crosslinked resin by using a solvent, and then removing stress, oil and cleaning;
preparing a multi-cell metal micro-nano structure: and depositing a plurality of layers of metal on the surface of the polymer forming the three-dimensional multi-cell polymer micro-nano structure by adopting a physical deposition method, a chemical deposition method or a physical and chemical combined deposition method to prepare the high-toughness multi-cell metal micro-nano structure.
In the above scheme, the photosensitive resin comprises a prepolymer, a diluent, and a photoinitiator.
In the above scheme, the two-photon polymerization process parameters are as follows: pulse width 80 fs; average pulse energy is 0.10-0.25 nJ; the repetition frequency is 80 MHz; the scanning speed is 5mm/s, and the focal diameter is 0.35 mu m; the scanning step pitch is 0.4-0.7 μm.
In the above scheme, the metal is a combination of two or more metals.
In the scheme, in the step of preparing the three-dimensional multi-cell polymer micro-nano structure, the stress removal is carried out by mixing the components in a volume ratio of 1: 3 for 30min in acetone aqueous solution, or treating for 2h by using an oven at the constant temperature of 80 ℃.
In the scheme, in the step of preparing the three-dimensional multi-cellular polymer micro-nano structure, the oil removal is carried out by soaking in absolute ethyl alcohol for 30min, or soaking in a mixed solution containing 25g/L of sodium hydroxide, 30g/L of sodium carbonate and 50g/L of sodium phosphate for 30min at 50 ℃.
In the scheme, the physical deposition method in the preparation step of the multi-cell metal micro-nano structure is laser beam evaporation plating, resistance evaporation plating, ion plating or magnetron sputtering plating.
In the scheme, the chemical deposition method in the preparation step of the multi-cell metal micro-nano structure is chemical plating, electroplating, a chemical reduction method or chemical vapor deposition.
A light high-strength and high-toughness multi-cell metal micro-nano structure is prepared by the preparation method of the light high-strength and high-toughness multi-cell metal micro-nano structure.
Compared with the prior art, the invention has the beneficial effects that: the novel composite manufacturing technology of the two-photon polymerization and deposition process can realize the manufacturing of a three-dimensional micro-nano structure with higher resolution, and is convenient for controlling the composition and the characteristics of materials forming the three-dimensional micro-nano structure, thereby obtaining high performance or multiple functions; the multi-cell metal micro-nano structure prepared by the invention integrates the geometric structure enhancement effect and the synergistic enhancement effect of the inherent properties of multi-layer multi-performance metal, can effectively improve the coordinated deformation capability and enhance the toughness; the method is beneficial to reducing the use of metal and compounds thereof while obtaining the high-toughness three-dimensional micro-nano structure, and can reduce the structure quality and the production cost; the method has simple process and easy operation, and can realize digital and automatic precise micro-nano manufacturing.
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FIG. 1 is a schematic diagram of a preparation process of a multi-cell metal micro-nano structure.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited thereto.
As shown in fig. 1, the method for preparing a light, high-strength and high-toughness multi-cell metal micro-nano structure of the invention uses a new composite manufacturing technology combining two-photon polymerization and deposition process to scan a liquid polymer layer by using femtosecond laser according to a designed three-dimensional model of the three-dimensional multi-cell micro-nano structure to enable the liquid polymer to generate polymerization reaction to form a three-dimensional high polymer micro-nano structure, then deposits multiple layers of metal on the surface of the high polymer to form a composite metal layer with gradient change of mechanical properties, and prepares the high-strength and high-toughness multi-cell metal micro-nano structure, and comprises the following steps:
establishing a micro-nano structure three-dimensional model: establishing a three-dimensional model of a three-dimensional multi-cell micro-nano structure, and discretely layering the three-dimensional model by using model layering software;
preparing photosensitive resin: preparing photosensitive resin meeting two-photon polymerization;
selection of laser processing system: selecting a proper laser processing system;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing a laser processing system to enable laser to be incident into photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, dissolving the non-crosslinked resin by using a solvent, and then removing stress, oil and cleaning;
preparing a multi-cell metal micro-nano structure: and depositing a plurality of layers of metal materials on the surface of the three-dimensional multi-cell polymer micro-nano structure by adopting a physical deposition method or a chemical deposition method or a physical and chemical combined deposition method to prepare the high-toughness multi-cell metal micro-nano structure with the mechanical property changing in a gradient manner from inside to outside.
The metal material is a combination of two or more metals, and each metal is deposited on the surface of a polymer forming the three-dimensional multi-cell polymer micro-nano structure in sequence to form a composite metal layer, so that the toughness is improved.
Preferably, the photosensitive resin comprises a prepolymer, a diluent and a photoinitiator.
Preferably, the laser processing system comprises a femtosecond laser, a light path transmission control device, a confocal real-time monitoring device, a three-dimensional mobile platform and a control device.
Preferably, the transmission control device comprises an optical shutter, a beam expander, a lens, a reflector, a focusing objective lens with a large numerical aperture (NA ═ 1.4 oil immersion) and a high magnification (100 ×); (ii) a The high magnification focusing objective lens is 100 x.
Preferably, the two-photon polymerization process parameters are as follows: pulse width 80 fs; average pulse energy is 0.10-0.25 nJ; the repetition frequency is 80 MHz; the scanning speed is 5mm/s, and the focal diameter is 0.35 mu m; the scanning step pitch is 0.4-0.7 μm.
Preferably, the solvent for dissolving the uncrosslinked resin in the preparation step of the three-dimensional multi-cellular polymer micro-nano structure is alcohol.
Preferably, in the step of preparing the three-dimensional multi-cell polymer micro-nano structure, the stress removal is performed by mixing the components in a volume ratio of 1: 3 for 30min in acetone aqueous solution, or treating for 2h by using an oven at the constant temperature of 80 ℃.
Preferably, in the step of preparing the three-dimensional multi-cellular polymer micro-nano structure, the degreasing step is to soak the three-dimensional multi-cellular polymer micro-nano structure in absolute ethyl alcohol for 30min, or soak the three-dimensional multi-cellular polymer micro-nano structure in a mixed solution containing 25g/L of sodium hydroxide, 30g/L of sodium carbonate and 50g/L of sodium phosphate for 30min at 50 ℃.
Preferably, the physical deposition method in the preparation step of the multi-cell metal micro-nano structure is laser beam evaporation plating, resistance evaporation plating, ion plating or magnetron sputtering plating.
Preferably, in the preparation step of the multi-cell metal micro-nano structure, a chemical deposition method is chemical plating, electroplating, a chemical reduction method or chemical vapor deposition.
Preferably, the deposition method of physical and chemical combination in the preparation step of the multi-cell metal micro-nano structure is a method of random combination between the physical deposition method and the chemical deposition method.
Example 1
Establishing a micro-nano structure three-dimensional model: designing a micro-nano manufactured three-dimensional model, and utilizing Solidworks software to discretely layer the three-dimensional model.
Preparing photosensitive resin: preparing a liquid polymer, namely photosensitive resin, wherein the photosensitive resin comprises methyl methacrylate, poly dipentaerythritol hexaacrylate and a photoinitiator, and the methyl methacrylate, the poly dipentaerythritol hexaacrylate and the photoinitiator are mixed according to the mass ratio of 49:49: 2;
selection of laser processing system: selecting a laser processing system which comprises a femtosecond laser, a light path transmission control device, a confocal real-time monitoring device, a three-dimensional mobile platform and a control device;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters, wherein the pulse width is 80fs, the average pulse energy is 0.10nJ, the repetition frequency is 80MHz, the scanning speed is 5mm/s, the focal diameter is 0.35 mu m, and the scanning step pitch is 0.4 mu m;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing the laser processing system to enable laser to be incident into the photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, taking out the cured three-dimensional multi-cell polymer micro-nano structure after micro-nano manufacturing is finished, putting the cured three-dimensional multi-cell polymer micro-nano structure into alcohol to dissolve the uncrosslinked resin, and then putting the cured three-dimensional multi-cell polymer micro-nano structure into VAcetone (II)：VWater (W)1: 3, removing stress after 30min of solution, and finally soaking the mixture in absolute ethyl alcohol for 30min to remove oil;
preparing a multi-cell metal micro-nano structure: the three-dimensional multi-cell polymer micro-nano structure is placed in a coating chamber, metal copper and nickel are sequentially coated on the surface of a polymer base material forming the three-dimensional micro-nano structure by utilizing a laser beam evaporation coating technology, the toughness is improved, and the light high-toughness three-dimensional multi-cell metal micro-nano structure is prepared.
Example 2
Establishing a micro-nano structure three-dimensional model: designing a micro-nano manufactured three-dimensional model, and utilizing Solidworks software to discretely layer the three-dimensional model.
Preparing photosensitive resin: preparing a liquid polymer, namely a photosensitive resin, wherein the photosensitive resin comprises butyl methacrylate, propoxylated trimethylolpropane triacrylate and a photoinitiator; mixing butyl methacrylate, propoxylated trimethylolpropane triacrylate and a photoinitiator according to the mass ratio of 36:56: 8;
selection of laser processing system: selecting a laser processing system which comprises a femtosecond laser, a light path transmission control device, a confocal real-time monitoring device, a three-dimensional mobile platform and a control device;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters, wherein the pulse width is 80fs, the average pulse energy is 0.15nJ, the repetition frequency is 80MHz, the scanning speed is 5mm/s, the focal diameter is 0.35 mu m, and the scanning step pitch is 0.5 mu m;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing the laser processing system to enable laser to be incident on the photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, taking out the cured three-dimensional multi-cell polymer micro-nano structure after micro-nano manufacturing is finished, putting the cured three-dimensional multi-cell polymer micro-nano structure into alcohol to dissolve the non-crosslinked resin, then treating the three-dimensional multi-cell polymer micro-nano structure for 2 hours at the constant temperature of 80 ℃ by using an oven, removing stress, and finally soaking the three-dimensional multi-cell polymer micro;
preparing a multi-cell metal micro-nano structure: the three-dimensional multi-cell polymer micro-nano structure is placed in a coating chamber, and metal aluminum and nickel are sequentially coated on the surface of a high polymer base material forming the three-dimensional micro-nano structure by using a resistance evaporation coating technology, so that the toughness is improved, and the light high-toughness three-dimensional multi-cell metal micro-nano structure is prepared.
Example 3
Establishing a micro-nano structure three-dimensional model: designing a three-dimensional model manufactured in a micro-nano mode, and discretely layering the three-dimensional model by using Skeinfoform software.
Preparing photosensitive resin: preparing a liquid polymer, namely photosensitive resin, wherein the photosensitive resin comprises a trifunctional acrylate monomer, a photoinitiator and a styrene/acrylonitrile copolymer, and the mass ratio of styrene to acrylonitrile is 75: 25; the trifunctional acrylate monomer, the photoinitiator and the styrene/acrylonitrile copolymer are mixed according to the mass ratio of 70:0.1: 29.9;
selection of laser processing system: selecting a laser processing system which comprises a femtosecond laser, a light path transmission control device, a confocal real-time monitoring device, a three-dimensional mobile platform and a control device;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters, wherein the pulse width is 80fs, the average pulse energy is 0.2nJ, the repetition frequency is 80MHz, the scanning speed is 5mm/s, the focal diameter is 0.35 mu m, and the scanning step pitch is 0.6 mu m;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing the laser processing system to enable laser to be incident into the photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, taking out the cured three-dimensional micro-nano structure after micro-nano manufacturing is finished, putting the cured three-dimensional micro-nano structure into alcohol to dissolve the uncrosslinked resin, and then putting the cured three-dimensional micro-nano structure into a VAcetone (II)：VWater (W)1: 3 for 30min, removing stress, and finally soaking in a mixed solution of 25g/L of sodium hydroxide, 30g/L of sodium carbonate and 50g/L of sodium phosphate at 50 ℃ for 30min to remove oil;
preparing a multi-cell metal micro-nano structure: placing the three-dimensional multi-cellular polymer micro-nano structure in a chemical copper plating solution, and plating metal copper on the surface of a high polymer base material forming the three-dimensional micro-nano structure by chemical plating;
and placing the three-dimensional multi-cell polymer micro-nano structure plated with copper into a coating chamber, and depositing metal titanium on the surface of the substrate material plated with copper by magnetron sputtering to improve the toughness, thereby preparing the light high-toughness three-dimensional multi-cell metal micro-nano structure.
Example 4
Establishing a micro-nano structure three-dimensional model: designing a micro-nano manufactured three-dimensional model, and discretely layering the three-dimensional model by using Ferry software;
preparing photosensitive resin: preparing a liquid polymer, namely photosensitive resin, wherein the photosensitive resin comprises a trifunctional acrylate monomer, a photoinitiator and a styrene/acrylonitrile copolymer, and the mass ratio of styrene to acrylonitrile is 75: 25; the trifunctional acrylate monomer, the photoinitiator and the styrene/acrylonitrile copolymer are mixed according to the mass ratio of 70:0.1: 29.9;
selection of laser processing system: selecting a laser processing system which comprises a femtosecond laser, a light path transmission control device, a confocal real-time monitoring device, a three-dimensional mobile platform and a control device;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters, wherein the pulse width is 80fs, the average pulse energy is 0.25nJ, the repetition frequency is 80MHz, the scanning speed is 5mm/s, the focal diameter is 0.35 mu m, and the scanning step pitch is 0.7 mu m;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing the laser processing system to enable laser to be incident into the photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, taking out the cured three-dimensional micro-nano structure after micro-nano manufacturing is finished, putting the cured three-dimensional micro-nano structure into alcohol to dissolve the uncrosslinked resin, and then putting the cured three-dimensional micro-nano structure into a VAcetone (II)：VWater (W)1: 3, removing stress after 30min of solution, and finally soaking the mixture in absolute ethyl alcohol for 30min to remove oil;
preparing a multi-cell metal micro-nano structure: placing the three-dimensional multi-cell polymer micro-nano structure into a coating chamber, and depositing metal aluminum on the surface of a high polymer base material forming the three-dimensional micro-nano structure by utilizing magnetron sputtering;
placing the aluminized three-dimensional micro-nano structure in a chemical copper plating solution, and plating metal copper on the surface of the aluminized base material by using chemical plating;
and placing the aluminized/copper three-dimensional micro-nano structure in an electroplating nickel solution, and plating metal nickel on the surface of the aluminized/copper base material by electroplating, so that the toughness is improved, and the light high-toughness three-dimensional multi-cell metal micro-nano structure is prepared.
It should be understood that although the present description has been described in terms of various embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and those skilled in the art will recognize that the embodiments described herein may be combined as suitable to form other embodiments, as will be appreciated by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. A preparation method of a lightweight high-toughness multi-cell metal micro-nano structure is characterized by comprising the following steps:
establishing a micro-nano structure three-dimensional model: establishing a three-dimensional model of a three-dimensional multi-cell micro-nano structure, and performing discrete layering;
preparing photosensitive resin: preparing a two-photon polymerized photosensitive resin;
selection of laser processing system: selecting a laser processing system;
setting two-photon polymerization process parameters: setting two-photon polymerization process parameters;
preparing a three-dimensional multi-cell polymer micro-nano structure: utilizing the laser processing system to enable laser to be incident into the photosensitive resin, carrying out two-photon polymerization to obtain a three-dimensional multi-cell polymer micro-nano structure, dissolving the non-crosslinked resin by using a solvent, and then removing stress, oil and cleaning;
preparing a multi-cell metal micro-nano structure: and depositing a plurality of layers of metal on the surface of the polymer forming the three-dimensional multi-cell polymer micro-nano structure by adopting a physical deposition method, a chemical deposition method or a physical and chemical combined deposition method to prepare the high-toughness multi-cell metal micro-nano structure.
2. The preparation method of the light-weight high-toughness multi-cell metal micro-nano structure according to claim 1, wherein the photosensitive resin comprises a prepolymer, a diluent and a photoinitiator.
3. The preparation method of the light high-toughness multi-cell metal micro-nano structure according to claim 1, wherein the two-photon polymerization process parameters are as follows: pulse width 80 fs; average pulse energy is 0.10-0.25 nJ; the repetition frequency is 80 MHz; the scanning speed is 5mm/s, and the focal diameter is 0.35 mu m; the scanning step pitch is 0.4-0.7 μm.
4. The preparation method of the light high-strength and toughness multi-cell metal micro-nano structure according to claim 1, wherein the stress relief in the preparation step of the three-dimensional multi-cell polymer micro-nano structure is performed by performing stress relief on a polymer material in a volume ratio of 1: 3 for 30min in acetone aqueous solution, or treating for 2h by using an oven at the constant temperature of 80 ℃.
5. The method for preparing the light high-toughness multi-cell metal micro-nano structure according to claim 1, wherein the degreasing step in the preparation step of the three-dimensional multi-cell polymer micro-nano structure is soaking in absolute ethyl alcohol for 30min, or soaking in a mixed solution comprising 25g/L of sodium hydroxide, 30g/L of sodium carbonate and 50g/L of sodium phosphate at 50 ℃ for 30 min.
6. The preparation method of the light high-strength and toughness multi-cell metal micro-nano structure according to claim 1, wherein in the preparation step of the multi-cell metal micro-nano structure, a physical deposition method is laser beam evaporation plating, resistance evaporation plating, ion plating or magnetron sputtering plating.
7. The preparation method of the light high-strength and high-toughness multi-cell metal micro-nano structure according to claim 1, wherein in the preparation step of the multi-cell metal micro-nano structure, a chemical deposition method is chemical plating, electroplating, a chemical reduction method or chemical vapor deposition.
8. A light high-strength and high-toughness multi-cell metal micro-nano structure is characterized by being prepared by the preparation method of the light high-strength and high-toughness multi-cell metal micro-nano structure according to any one of claims 1 to 7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745447A (en) * | 2020-12-28 | 2021-05-04 | 江苏大学 | Micro-nano negative Poisson's ratio structure and two-photon polymerization preparation method thereof |
| CN114018684A (en) * | 2021-10-28 | 2022-02-08 | 华中科技大学 | Bionic three-dimensional hierarchical micro-nano structure integrated micro-device and preparation and application thereof |
| CN114613455A (en) * | 2022-02-25 | 2022-06-10 | 江苏大学 | Polycrystalline-like structure porous material and design method thereof |
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