CN112745447A - Micro-nano negative Poisson's ratio structure and two-photon polymerization preparation method thereof - Google Patents
Micro-nano negative Poisson's ratio structure and two-photon polymerization preparation method thereof Download PDFInfo
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- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003504 photosensitizing agent Substances 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000178 monomer Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
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- 229920001577 copolymer Polymers 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000005237 degreasing agent Methods 0.000 claims description 2
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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Abstract
A micro-nano negative Poisson' S ratio structure and a two-photon polymerization preparation method thereof are provided, the method comprises the steps of S1: designing a two-photon polymer structure model with a negative Poisson ratio structure, and discretely layering the model; step S2: preparing photosensitive resin meeting two-photon polymerization; step S3: fully mixing photosensitive resin and metal ion solution and putting the mixture into a laser printing pool; step S4: setting laser processing parameters; step S5: implementing a two-photon polymerization process to obtain a micro-nano negative Poisson's ratio structure; step S6: dissolving the non-crosslinked resin, and then removing stress, oil, cleaning and drying; step S7: and testing the performance of the obtained micro-nano negative Poisson ratio structure. On the premise that photosensitive resin meets two-photon polymerization, a designed negative Poisson ratio structure is precisely polymerized by femtosecond laser, and then the performance of the micro-nano negative Poisson ratio structure is improved by dissolving metal ions, so that a feasible thought is provided for high-quality and high-precision preparation of the micro-nano negative Poisson ratio structure with controllable shape.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a micro-nano negative Poisson's ratio structure and a two-photon polymerization preparation method thereof.
Background
Negative poisson's ratio material expands laterally when uniaxially stretched in the elastic range, and contracts laterally when compressed, and has a particular geometry, such as concave, chiral, rotating, etc., which imparts excellent physical and mechanical properties, such as ultra-high specific strength and modulus, fracture toughness, indentation resistance, and good energy absorption. In recent years, a lot of scholars at home and abroad carry out extensive research on negative poisson ratio structures and materials, but the existing related research mainly focuses on negative poisson ratio materials with macroscopic sizes of millimeter level and above, and the research on the manufacturing and application of micro-nano level negative poisson ratio structures is still in the starting stage. Because the negative poisson structure is generally complex in structure and has activity at a cell body connecting interface, great challenges are brought to micro-nano-scale precision preparation.
Disclosure of Invention
The invention aims to provide a technical scheme for the development of a micro-nano negative Poisson's ratio structure and provides a two-photon polymerization preparation method of a shape-controllable micro-nano negative Poisson's ratio structure. The technical scheme of the invention is as follows: designing a micro-nano negative Poisson's ratio structural model to be processed by utilizing three-dimensional software, converting the micro-nano negative Poisson's ratio structural model into point cloud data which can be used for processing, and then controlling the movement of a three-dimensional precision moving system through a corresponding computer recognizable instruction; simultaneously preparing liquid photosensitive resin and a reinforced metal ion mixed solution, performing point-by-point scanning → layer-by-layer scanning on the oil-immersed liquid mixed solution by adopting a femtosecond laser experimental device, utilizing the cooperation of a digital galvanometer and a one-dimensional piezoelectric platform, controlling the movement of a three-dimensional precise moving system and the closing of an optical gate by a computer, observing a real-time processing state by a real-time monitoring system of a CCD (charge coupled device), and realizing the processing of a micro-nano negative Poisson ratio structure. According to the invention, a feasible idea is provided for high-quality and high-precision preparation of the shape-controllable micro-nano negative Poisson ratio structure by adjusting the negative Poisson ratio 3D structure and the type of the metal solution.
A two-photon polymerization preparation method of a micro-nano negative Poisson's ratio structure comprises the following steps:
step S1: designing a two-photon polymer structure model with a negative Poisson ratio structure through software, and discretely layering the model by using the software;
step S2: preparing photosensitive resin meeting two-photon polymerization;
step S3: fully mixing photosensitive resin and metal ion solution and putting the mixture into a laser printing pool;
step S4: setting laser processing parameters: pulse width, average pulse energy, repetition frequency, center wavelength, scan rate, and focal diameter;
step S5: implementing a two-photon polymerization process to obtain a micro-nano negative Poisson's ratio structure;
step S6: dissolving the non-crosslinked resin, and then removing stress, oil, cleaning and drying;
step S7: and testing the performance of the obtained micro-nano negative Poisson ratio structure.
In the above scheme, the two-photon polymer structure model in step S1 is a 3D micro-nano negative poisson' S ratio structure.
In the above scheme, the model layering software in step S2 is Solidworks, skein form, or Ferry.
In the above scheme, the photosensitive resin in step S2 includes a photoinitiator, a photosensitizer, a resin monomer, a crosslinking agent, and a diluent.
In the above scheme, in step S2, the photosensitive resin is: methyl Methacrylate, crosslinking agent DPE-6A, photoinitiator Benzil and photosensitizer 2-Benzil-2-dimethlamino-4-morpholino butyrophenon are mixed according to the proportion of 45:45:5:5,
or Methyl Methacrylate (Methyl Methacrylate, cross-linking agent DPE-6A, photoinitiator Benzil and photosensitizer 2-Benzil-2-dimethlamino-4-morpholinobutyrophenon in a ratio of 40:40:10:10,
or mixing a trifunctional acrylate monomer, a photoinitiator DPABz and a styrene/acrylonitrile copolymer according to a ratio of 75:1:24, wherein the trifunctional acrylate monomer is SR368 or SR9008, and the ratio of the styrene/acrylonitrile copolymer is 75: 25.
in the above scheme, the metal ion solution in step S3 is a silver nitrate solution, an iron chloride solution, or a copper sulfate solution.
In the foregoing solution, the laser processing parameters in step S4 are: the pulse width is 80fs, the average pulse energy is 0.10-0.45nJ, the repetition frequency is 40-80MHz, the central wavelength is 780nm, the scanning speed is 3-8mm/s, the large numerical aperture NA is 1.4 oil immersion and the focusing objective lens with high magnification factor of 100 x.
In the foregoing solution, the step S5 specifically includes: the method comprises the steps of scanning a mixed solution of photosensitive resin and metal ions point by point and layer by adopting a femtosecond laser experimental device, controlling the movement of a three-dimensional precise moving system and the closing of an optical gate by utilizing the cooperation of a digital galvanometer and a one-dimensional piezoelectric platform through a computer, and observing a real-time processing state through a real-time monitoring system of a CCD (charge coupled device) to obtain a micro-nano negative Poisson's ratio structure.
In the foregoing solution, the step S6 specifically includes: dissolving the uncrosslinked resin by using alcohol; by using VAcetone (II)：VWater (W)1: 3, soaking for 30min or treating for 3h by using an oven at the constant temperature of 80 ℃ to remove stress; the degreasing agent contains absolute ethyl alcohol, and the soaking time is 30 min; or 25g/L of sodium hydroxide, 30g/L of sodium carbonate, 50g/L of sodium phosphate, 45-55 ℃ and 30min of soaking time; or 15g/L potassium dichromate, 300mL/L concentrated sulfuric acid and 45-55 ℃, and the soaking time is 30 min.
In the foregoing solution, the performance of the negative poisson' S ratio structure in step S7 includes: tensile properties, shear modulus, elastic modulus, damping properties, fracture resistance or resilience toughness.
A micro-nano negative Poisson's ratio structure is prepared according to a two-photon polymerization preparation method of the micro-nano negative Poisson's ratio structure.
Compared with the prior art, the invention has the beneficial effects that: the invention aims at high-precision forming of the micro-nano level negative Poisson's ratio structure, so as to break through the bottleneck of the manufacturing technology of the micro-nano negative Poisson's ratio structure and provide specific technical support for the application of the micro-nano negative Poisson's ratio structure. According to the invention, based on a high-precision two-photon polymerization method, a metal ion solution is added for regulation and control, specific material proportion, polymerization process parameters and post-treatment parameters are given, a micro-nano negative Poisson's ratio structure with controllable shape is prepared, and good negative Poisson's ratio performance is displayed. The performance of the micro-nano negative Poisson ratio structure prepared by the method is verified, the property of the material with the good negative Poisson ratio is determined, and the feasibility and the effectiveness of the invention are proved.
Drawings
FIG. 1 is a schematic view of the preparation process of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and detailed description, but the scope of the present invention is not limited thereto.
As shown in fig. 1, a two-photon polymerization preparation method of a micro-nano negative poisson ratio structure comprises the steps of designing a pre-printed micro-nano negative poisson ratio structure model and three-dimensional model slice layering, preparing two-photon absorption photosensitive resin, dissolving metal ions, carrying out two-photon polymerization, detecting the performance of the micro-nano negative poisson ratio structure and the like. The model slice layering refers to the discrete segmentation of a design model by using software such as Solidworks, Skeinfoform or Ferry; the preparation of the two-photon absorption photosensitive resin refers to that a monomer, a photosensitizer, a photoinitiator, a diluent and the like are mixed to prepare the resin meeting the two-photon absorption property; the two-photon polymerization refers to that photosensitive resin which accords with the two-photon absorption property absorbs two photons to carry out polymerization reaction; dissolving the metal ion solution into the photosensitive resin means dissolving the reinforcing ions into the photosensitive resin for polymerization to perform the reinforcing function. On the premise that photosensitive resin meets two-photon polymerization, a designed negative Poisson ratio structure is precisely polymerized by femtosecond laser, and then the performance of the micro-nano negative Poisson ratio structure is improved by dissolving metal ions.
Example 1
Step S1: designing a preprinted micro-nano negative Poisson ratio structure model, and discretely layering the model by utilizing Solidworks software.
Step S2: preparing a liquid polymer, namely photosensitive resin, which is prepared from Methyl Methacrylate, a cross-linking agent DPE-6A, a photoinitiator Benzil and a photosensitizer 2-Benzil-2-dimethlamino-4-morpholino butyrophenon according to the proportion of 45:45:5: 5;
step S3: dissolving silver nitrate solution into photosensitive resin and putting the photosensitive resin into a printing pool;
step S4: selecting laser processing parameters: pulse width 80fs, average pulse energy 0.10nJ, repetition frequency 80MHz, center wavelength 780nm, scanning speed 3mm/s, and focal diameter 0.35 μm;
step S5: carrying out two-photon polymerization to obtain a micro-nano negative Poisson's ratio structure;
step S6: after printing, the solidified material is taken out and placed in VAcetone (II)：VWater (W)1: 3, removing stress after the solution is used for 30min, taking out the material, soaking the material in absolute ethyl alcohol for 30min to remove oil, and then placing the material in a drying oven to dry;
step S7: the mechanical property of the obtained negative Poisson ratio structure is tested, the equivalent Poisson ratio is-0.1 to-0.8, the elastic modulus is 1MPa to 8MPa, the shear modulus is 1.5MPa to 10.8MPa, the compression strength is 0.2 to 7MPa, the tensile strength is 1.8 to 3.9MPa, and the impact strength is 1.9 to 9.6 MPa. The cell wall branch diameter is 200-500 nm. The manufacturing quality of the micro-nano negative Poisson ratio structure is shown, and the feasibility and the effectiveness of the invention are demonstrated.
Example 2
Step S1: designing a preprinted micro-nano negative Poisson ratio structural model, and discretely layering the model by using Skeinfoform software.
Step S2: preparing a liquid polymer, namely photosensitive resin, which is prepared from Methyl Methacrylate, a cross-linking agent DPE-6A, a photoinitiator Benzil and a photosensitizer 2-Benzil-2-dimethlamino-4-morpholino butyrophenon according to the proportion of 40:40:10: 10;
step S3: dissolving ferric chloride solution into photosensitive resin and putting the photosensitive resin into a printing pool;
step S4: selecting laser processing parameters: pulse width 80fs, average pulse energy 0.20nJ, repetition frequency 80MHz, center wavelength 780nm, scanning speed 5mm/s, and focal diameter 0.35 μm;
step S5: carrying out two-photon polymerization to obtain a micro-nano negative Poisson's ratio structure;
step S6: after printing, taking out the cured material, treating the cured material for 3 hours by using an oven at the constant temperature of 80 ℃, removing stress, taking out the material, removing oil by using 25g/L of sodium hydroxide, 30g/L of sodium carbonate, 50g/L of sodium phosphate and 45 ℃, soaking for 30min, and then placing the material in a drying oven for drying;
step S7: the mechanical property of the obtained negative Poisson ratio structure is tested, the equivalent Poisson ratio is-0.15 to-0.6, the elastic modulus is 0.5MPa to 6MPa, the shear modulus is 2MPa to 10MPa, the compression strength is 1.2 to 6.5MPa, the tensile strength is 2MPa to 5MPa, and the impact strength is 1.5MPa to 8 MPa. The cell wall branch diameter is 220-480 nm. The manufacturing quality of the micro-nano negative Poisson ratio structure is shown, and the further shape regulation of the micro-nano negative Poisson ratio structure is demonstrated by properly adjusting the process parameters.
Example 3
Step S1: designing a preprinted micro-nano negative Poisson's ratio structure model, and discretely layering the micro-nano negative Poisson's ratio structure model by using Ferry software.
Step S2: the prepared liquid polymer, namely photosensitive resin, is composed of three components, namely trifunctional acrylate monomers SR368 and SR9008, a photoinitiator DPABz and a styrene/acrylonitrile copolymer 75:25 according to a ratio of 75:1: 24;
step S3: dissolving a copper sulfate solution into photosensitive resin and putting the photosensitive resin into a printing pool;
step S4: selecting laser processing parameters: pulse width 80fs, average pulse energy 0.40nJ, repetition frequency 80MHz, center wavelength 780nm, scanning speed 7mm/s, and focal diameter 0.35 μm;
step S5: carrying out two-photon polymerization to obtain a micro-nano negative Poisson's ratio structure;
step S6: after printing, the solidified material is taken out and placed in VAcetone (II)：VWater (W)1: 3 for 30min, removing stress, taking out material, and treating with 15g/L potassium dichromate and 300mL/L concentrated sulfuric acid 5Removing oil at 0 deg.C, soaking for 30min, and oven drying in a drying oven;
step S7: the mechanical property of the obtained negative Poisson ratio structure is tested, the equivalent Poisson ratio is-0.2 to-0.9, the elastic modulus is 0.2MPa to 10MPa, the shear modulus is 5MPa to 12.5MPa, the impact strength is 3.6 to 8MPa, the compression strength is 0.2 to 15MPa, and the tensile strength is 1.2 to 12.4 MPa. The diameter of the cell wall branches is 180-450 nm. The result shows good negative Poisson's ratio property and more ideal micro-nano negative Poisson's ratio structure manufacturing quality, which explains the effectiveness of the invention and the operability of flexibly regulating and controlling the shape property by properly adjusting the material proportion and the process parameters.
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 (10)
1. A two-photon polymerization preparation method of a micro-nano negative Poisson's ratio structure is characterized by comprising the following steps:
step S1: designing a two-photon polymer structure model with a negative Poisson ratio structure through software, and discretely layering the model by using the software;
step S2: preparing photosensitive resin meeting two-photon polymerization;
step S3: fully mixing photosensitive resin and metal ion solution and putting the mixture into a laser printing pool;
step S4: setting laser processing parameters: pulse width, average pulse energy, repetition frequency, center wavelength, scan rate, and focal diameter;
step S5: implementing a two-photon polymerization process to obtain a micro-nano negative Poisson's ratio structure;
step S6: dissolving the non-crosslinked resin, and then removing stress, oil, cleaning and drying;
step S7: and testing the performance of the obtained micro-nano negative Poisson ratio structure.
2. The two-photon polymerization preparation method of the micro-nano negative poisson 'S ratio structure according to claim 1, wherein the two-photon polymer structure model in the step S1 is a 3D micro-nano negative poisson' S ratio structure.
3. The method for preparing the micro-nano negative Poisson' S ratio structure through two-photon polymerization according to claim 1, wherein the model layering software in the step S2 is Solidworks, Skeinfoform or Ferry.
4. The method for preparing a micro-nano negative Poisson' S ratio structure by two-photon polymerization according to claim 1, wherein the photosensitive resin in the step S2 comprises a photoinitiator, a photosensitizer, a resin monomer, a cross-linking agent and a diluent.
5. The two-photon polymerization preparation method of the micro-nano negative Poisson' S ratio structure according to claim 4, wherein the photosensitive resin in the step S2 is: methyl Methacrylate, crosslinking agent DPE-6A, photoinitiator Benzil and photosensitizer 2-Benzil-2-dimethlamino-4-morpholino butyrophenon are mixed according to the proportion of 45:45:5:5,
or Methyl Methacrylate (Methyl Methacrylate, cross-linking agent DPE-6A, photoinitiator Benzil and photosensitizer 2-Benzil-2-dimethlamino-4-morpholinobutyrophenon in a ratio of 40:40:10:10,
or mixing a trifunctional acrylate monomer, a photoinitiator DPABz and a styrene/acrylonitrile copolymer according to a ratio of 75:1:24, wherein the trifunctional acrylate monomer is SR368 or SR9008, and the ratio of the styrene/acrylonitrile copolymer is 75: 25.
6. the method for preparing a two-photon polymerization with a micro-nano negative Poisson' S ratio structure according to claim 1, wherein the metal ion solution in the step S3 is a silver nitrate solution, an iron chloride solution or a copper sulfate solution.
7. The two-photon polymerization preparation method of the micro-nano negative Poisson' S ratio structure according to claim 1, wherein the laser processing parameters in the step S4 are as follows: the pulse width is 80fs, the average pulse energy is 0.10-0.45nJ, the repetition frequency is 40-80MHz, the central wavelength is 780nm, the scanning speed is 3-8mm/s, the large numerical aperture NA is 1.4 oil immersion and the focusing objective lens with high magnification factor of 100 x.
8. The two-photon polymerization preparation method of the micro-nano negative poisson' S ratio structure according to claim 1, wherein the step S5 is specifically: the method comprises the steps of scanning a mixed solution of photosensitive resin and metal ions point by point and layer by adopting a femtosecond laser experimental device, controlling the movement of a three-dimensional precise moving system and the closing of an optical gate by utilizing the cooperation of a digital galvanometer and a one-dimensional piezoelectric platform through a computer, and observing a real-time processing state through a real-time monitoring system of a CCD (charge coupled device) to obtain a micro-nano negative Poisson's ratio structure.
9. The two-photon polymerization preparation method of the micro-nano negative poisson' S ratio structure according to claim 1, wherein the step S6 is specifically: dissolving the uncrosslinked resin by using alcohol; by using VAcetone (II)：VWater (W)1: 3, soaking for 30min or treating for 3h by using an oven at the constant temperature of 80 ℃ to remove stress; the degreasing agent contains absolute ethyl alcohol, and the soaking time is 30 min; or 25g/L of sodium hydroxide, 30g/L of sodium carbonate, 50g/L of sodium phosphate, 45-55 ℃ and 30min of soaking time; or 15g/L potassium dichromate, 300mL/L concentrated sulfuric acid and 45-55 ℃, and the soaking time is 30 min.
10. A micro-nano negative poisson's ratio structure, characterized in that, the structure is prepared by the two-photon polymerization preparation method of the micro-nano negative poisson's ratio structure according to any one of claims 1-9.
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| CN115555578A (en) * | 2022-10-28 | 2023-01-03 | 华中科技大学 | Preparation method of three-dimensional micro-nano structure of metal and metal compound |
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| US20090206520A1 (en) * | 2008-02-19 | 2009-08-20 | Samsung Electronics Co., Ltd. | Photosensitive composition, microfabrication method using the same, and microfabricated structure thereof |
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| CN115555578A (en) * | 2022-10-28 | 2023-01-03 | 华中科技大学 | Preparation method of three-dimensional micro-nano structure of metal and metal compound |
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