CN110952124A - Antifouling titanium alloy material based on bionic super-smooth surface, and preparation method and application thereof - Google Patents
Antifouling titanium alloy material based on bionic super-smooth surface, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an antifouling titanium alloy material based on a bionic super-smooth surface, and a preparation method and application thereof. The preparation method comprises the following steps: processing a titanium alloy substrate by adopting an anodic oxidation method, and forming a nanostructure layer arranged in an array on the surface of the titanium alloy substrate, wherein the nanostructure layer comprises nanopores or nanotubes with different shapes and/or sizes; chemically modifying the titanium alloy substrate with the nanostructure layer by using a fluorosilane modifier; and applying a lubricant to the surface of the chemically modified titanium alloy substrate to obtain the antifouling titanium alloy material based on the bionic super-smooth surface. The bionic super-smooth surface can obviously reduce the attachment amount of bacteria on the surface of the titanium alloy, has obvious antibacterial attachment effect and excellent slow release effect, and meanwhile, the preparation method is an environment-friendly and efficient antifouling method, and has wider application prospect in the field of marine antifouling.
Description
Technical Field
The invention relates to an antifouling titanium alloy material, in particular to an antifouling titanium alloy material based on a bionic super-smooth surface and a preparation method thereof, and an antifouling method for preparing the bionic super-smooth surface on a titanium alloy, belonging to the technical field of marine antifouling coatings.
Background
Adhesion and deposition of marine organisms on marine equipment can lead to serious biofouling problems such as pipe plugging, increased ship gravity and frictional resistance, and corrosion of marine devices, which result in significant losses to the marine economy. Titanium alloy is widely applied to marine environment due to excellent mechanical property and corrosion resistance, but because of good biocompatibility, the titanium alloy faces more serious biological pollution problem, and the application in marine environment is limited. There are various current anti-fouling techniques, such as physical anti-fouling techniques including mechanical cleaning and ultrasonic removal, chemical anti-fouling and biological anti-fouling. Of these, chemical antifouling is the most effective and widely used antifouling method, and the antifouling mechanism is to use a composition containing a biological bactericide (such as tributyltin, Cu)2O, etc.) and toxic or microbicidal to achieve antifouling properties. However, biocides pose a hazard to the marine environment, leading to genetic alteration and death of marine organisms, ultimately threatening human health.
Disclosure of Invention
The invention aims to provide an antifouling titanium alloy material based on a bionic super-smooth surface, so as to overcome the defects of the prior art.
The invention further aims to provide a preparation method of the antifouling titanium alloy material based on the bionic super-smooth surface.
The invention also aims to provide application of the antifouling titanium alloy material based on the bionic super-smooth surface.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an antifouling titanium alloy material based on a bionic super-smooth surface, which comprises the following steps:
providing a titanium alloy substrate;
processing the titanium alloy substrate by adopting an anodic oxidation method, and forming a nanostructure layer arranged in an array on the surface of the titanium alloy substrate, wherein the nanostructure layer comprises nanopores or nanotubes, the diameter of each nanopore is 10-30 nm, the depth of each nanopore is 50-200 nm, the diameter of each nanotube is 30-200 nm, and the depth of each nanotube is 200-600 nm;
chemically modifying the titanium alloy substrate with the nanostructure layer by using a fluorosilane modifier;
and applying a lubricant to the surface of the chemically modified titanium alloy substrate to obtain the antifouling titanium alloy material based on the bionic super-smooth surface.
The embodiment of the invention also provides the antifouling titanium alloy material based on the bionic super-smooth surface prepared by the method.
The embodiment of the invention also provides an antifouling titanium alloy material based on the bionic super-smooth surface, which comprises a titanium alloy substrate and the bionic super-smooth surface arranged on the surface of the titanium alloy substrate, wherein the bionic super-smooth surface comprises a nano-structure layer, low-surface-energy substances modified on the surface and/or inside the nano-structure layer and a lubricant distributed on the surface and inside the nano-structure layer.
The embodiment of the invention also provides application of the antifouling titanium alloy material based on the bionic super-smooth surface in the field of marine antifouling.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a method for preparing a bionic super-smooth surface on the surface of a titanium alloy substrate to reduce biofouling on the surface of the titanium alloy, which comprises the steps of firstly preparing nano-hole or nano-tube structures with different shapes, diameters and depths on the surface of the titanium alloy by an anodic oxidation method, then carrying out chemical modification on the surface or the inside of the nano-structure, reducing the surface energy of the nano-structure by the chemical modification, enabling a lubricant to be more easily immersed into holes of the nano-structure, and finally injecting the lubricant. The attachment resistance experiment of bacteria proves that the bionic super-smooth surface can obviously reduce the attachment amount of bacteria on the surface of the titanium alloy, has obvious attachment resistance to the bacteria, and simultaneously, the nano structure of the bionic super-smooth surface and the used reagent have no toxicity to the bacteria, so the preparation method of the bionic super-smooth surface is a green, environment-friendly and efficient antifouling method and has wider application prospect in the field of marine antifouling;
2) the nano structure of the invention has the nano holes or nano tubes with controllable diameter and depth, can effectively prevent the lubricant in the nano structure from losing in a large amount, stores more lubricant, has the performance of slowly releasing the lubricant, and has better stability in water, thereby having long-term antifouling effect.
Drawings
FIG. 1 is a schematic diagram of a preparation method of an antifouling titanium alloy material based on a bionic super-smooth surface according to an exemplary embodiment of the invention.
Fig. 2a and 2b are scanning electron micrographs of the nanostructures prepared by anodization in example 1 of the present invention.
Fig. 2c and 2d are scanning electron micrographs of the nanostructures prepared by anodization in example 2 of the present invention.
Fig. 2e and 2f are scanning electron micrographs of the nanostructures prepared by anodization in example 3 of the present invention.
FIG. 2g is a scanning electron micrograph of a nanostructure prepared by anodic oxidation in comparative example 7 of the present invention.
FIG. 3 is a Raman spectrum of the titanium alloy material after the anodic oxidation obtained in examples 1, 2 and 3 of the present invention.
Fig. 4a and 4b are schematic diagrams illustrating changes of contact angle, rolling angle and rolling speed of the titanium alloy material (SLIPS-10V, SLIPS-15V, SLIPS-30V) with the bionic super-smooth surface obtained in example 1, example 2 and example 3 of the invention in an escherichia coli solution for soaking for different times.
FIGS. 5a and 5b are colony diagrams of the titanium alloy materials with bionic super-slippery surfaces obtained from the blank (b1) and the titanium alloy materials with bionic super-slippery surfaces obtained from inventive example 1(b8), comparative example 1(b2), comparative example 2(b5), example 2(b9), comparative example 3(b3), comparative example 4(b6), example 3(b10), comparative example 5(b4) and comparative example 6(b7) after being soaked in the E.coli solution for 1 day.
FIGS. 5c and 5d are colony diagrams of the titanium alloy materials with bionic super-slippery surfaces obtained from the blank (d1) and the titanium alloy materials with bionic super-slippery surfaces obtained from inventive example 1(d8), comparative example 1(d2), comparative example 2(d5), example 2(d9), comparative example 3(d3), comparative example 4(d6), example 3(d10), comparative example 5(d4) and comparative example 6(d7) after being soaked in the E.coli solution for 5 days.
FIGS. 5e and 5f are colony diagrams of titanium alloy materials with bionic super-slippery surfaces obtained from blank (f1) and inventive example 1(f8), comparative example 1(f2), comparative example 2(f5), example 2(f9), comparative example 3(f3), comparative example 4(f6), example 3(f10), comparative example 5(f4) and comparative example 6(f7) after being soaked in E.coli solution for 10 days.
Detailed Description
In view of the problem of biofouling of the current titanium alloy in service in the marine environment, the inventors of the present invention have made long-term research and extensive practice to provide a technical solution of the present invention, i.e., a method for preparing a biomimetic ultra-smooth surface on the surface of a titanium alloy to reduce biofouling of the surface of the titanium alloy. The technical solution, its implementation and principles, etc. will be further explained as follows.
The bionic anti-fouling is an anti-fouling method which is inspired by animals and plants such as sharkskin, pitcher plant and the like, prepares different micro/nano shapes on the surface of the material, is environment-friendly by interfering or blocking the adhesion process of marine organisms, and has wide application prospect. In nature, the bottleneck of the nepenthes secretes lubricant, so that the surface of the nepenthes has super-smooth performance, and insects can easily slide into the cage. Inspired by pitcher plant, the ultra-smooth surface is prepared on the surface of the titanium alloy to improve the anti-biological fouling capability of the surface of the titanium alloy. The anodic oxidation method is a common method for preparing a micro/nano structure on the surface of metal, and the micro/nano structure with ordered arrangement and controllable size can be obtained on the surface of the titanium alloy by adjusting electrochemical parameters. The lubricant is injected into the micro/nano structure through capillary force, and microorganisms are not easy to attach on the lubricant layer due to the super-slip performance of the lubricant, so that the surface of the titanium alloy has the function of preventing the attachment of the microorganisms.
As one aspect of the technical scheme of the invention, the invention relates to a preparation method of an antifouling titanium alloy material based on a bionic super-smooth surface, as shown in fig. 1, the preparation method comprises the following steps:
providing a titanium alloy substrate;
processing the titanium alloy substrate by adopting an anodic oxidation method, and forming a nanostructure layer arranged in an array on the surface of the titanium alloy substrate, wherein the nanostructure layer comprises nanopores or nanotubes, the diameter of each nanopore is 10-30 nm, the depth of each nanopore is 50-200 nm, the diameter of each nanotube is 30-200 nm, and the depth of each nanotube is 200-600 nm;
chemically modifying the titanium alloy substrate with the nanostructure layer by using a fluorosilane modifier;
and applying a lubricant to the surface of the chemically modified titanium alloy substrate to obtain the antifouling titanium alloy material based on the bionic super-smooth surface.
In some embodiments, the method of making comprises: and (3) carrying out anodic oxidation by adopting a constant-voltage direct-current power supply and taking the titanium alloy substrate as an anode, and forming a nanostructure layer on the surface of the titanium alloy substrate.
Further, the material of the nanostructure layer includes rutile type titanium dioxide, but is not limited thereto.
Further, the thickness of the nanostructure layer is 50-600 nm. The nano structure of the invention has the nano tubes or nano holes with controllable diameter and depth, can effectively prevent the lubricant in the nano structure from losing in a large amount, stores more lubricant, has the performance of slowly releasing the lubricant, and has better stability in water, thereby having long-term antifouling effect.
In some embodiments, the anodization process employs process conditions that include: the voltage is 5-50V, the electrolyte comprises a mixed solution of acid and fluoride, the temperature of anodic oxidation is 15-35 ℃, and the time of anodic oxidation is 3-60 min.
Further, the acid includes phosphoric acid and/or sulfuric acid.
Preferably, the concentration of the phosphoric acid or the sulfuric acid in the mixed solution is 0.1-1.0M.
Further, the fluoride includes any one or a combination of two or more of ammonium fluoride, sodium fluoride, hydrofluoric acid, and the like, but is not limited thereto.
Preferably, the concentration of the fluoride in the mixed solution is 0.03-0.30M.
In some embodiments, the fluorosilane modifier includes any one or a combination of two or more of 1H, 2H-perfluorodecaalkyltriethoxysilane, 1H, 2H-perfluorodecyltriethoxysilane, 1H, 2H-perfluorooctyltriethoxysilane, 1H, 2H-perfluorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, and the like, but is not limited thereto. The invention modifies the surface and the interior of the nanostructure layer by adopting the fluorosilane modifier, so that the lubricant can smoothly enter the nano holes or the nano tubes of the nanostructure.
Further, the concentration of the fluorosilane modifier in fluorosilane modifying liquid is 0.01-1 vol%, and the fluorosilane modifying liquid comprises mixed liquid of the fluorosilane modifier and ethanol.
In some embodiments, the temperature of the chemical modification is 20-60 ℃ and the time is 1-24 h.
Further, the preparation method further comprises the following steps: and drying the chemically modified titanium alloy material, wherein the drying temperature is 80-130 ℃, and the drying time is 0.5-4 h.
In some embodiments, the lubricant includes any one or a combination of two or more of Krytox perfluorooil, perfluoropolyether, silicone oil, ionic liquid, and the like, but is not limited thereto.
Further, the application amount of the lubricant is 1-10 mu L/cm2。
Further, the preparation method further comprises the following steps: applying a lubricant to the surface of the chemically modified titanium alloy substrate, injecting at least part of the lubricant into the nano-structure layer, drying to remove gas in the nano-structure layer, and then inclining by 10-90 degrees to remove redundant lubricant.
Further, in some more specific embodiments, the preparation method may include the steps of:
(1) preparation of nano structure by anodic oxidation method
And (3) placing the titanium alloy substrate on an anode by adopting a constant-voltage direct-current power supply to carry out anodic oxidation to obtain the nano structure.
(2) Chemical modification
And (3) soaking the anodized titanium alloy substrate in fluorosilane modifying liquid, and then drying in an oven.
(3) Lubricant injection
And injecting a lubricant into the chemically modified titanium alloy substrate, putting the chemically modified titanium alloy substrate into a vacuum drying oven to remove gas in the nano structure, and then obliquely placing the titanium alloy substrate to remove the redundant lubricant.
The invention also provides an antifouling titanium alloy material based on the bionic super-smooth surface, which is prepared by the method.
The invention also provides an antifouling titanium alloy material based on the bionic super-smooth surface, which comprises a titanium alloy substrate and the bionic super-smooth surface arranged on the surface of the titanium alloy substrate, wherein the bionic super-smooth surface comprises a nano-structure layer, low surface energy substances modified on the surface and/or inside the nano-structure layer and a lubricant distributed on the surface and inside the nano-structure layer.
Further, the contact angle between the antifouling titanium alloy material based on the bionic super-smooth surface and water is 115-125 degrees, the rolling angle is 2-5 degrees, and the sliding speed is 0.8-1.5 mm/s.
Further, after the antifouling titanium alloy material based on the bionic super-smooth surface is soaked in an escherichia coli solution for 10 days, a contact angle between the antifouling titanium alloy material and water is kept at 90-120 degrees, a rolling angle is 4-50 degrees, and a sliding speed is 0.01-0.4 mm/s.
Further, after the antifouling titanium alloy material based on the bionic super-smooth surface is soaked in an escherichia coli solution for 10 days, the attachment amount of escherichia coli on the surface is less than 32000 CFU/ml.
Further, the thickness of the nanostructure layer is 50-600 nm.
Further, the nanostructure layer comprises nanopores or nanotubes, wherein the diameter of the nanopores is 10-30 nm, the depth of the nanopores is 50-200 nm, the diameter of the nanotubes is 30-200 nm, and the depth of the nanotubes is 200-600 nm.
Further, the material of the nanostructure layer includes rutile type titanium dioxide, but is not limited thereto.
Further, the low surface energy material is derived from a fluorosilane modifier, and the fluorosilane modifier includes any one or a combination of two or more of 1H, 2H-perfluorodecaalkyltriethoxysilane, 1H, 2H-perfluorodecyltriethoxysilane, 1H, 2H-perfluorooctyltriethoxysilane, 1H, 2H-perfluorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, and the like, but is not limited thereto.
Further, the lubricant includes any one or a combination of two or more of Krytox perfluorooil, perfluoropolyether, silicone oil, ionic liquid, and the like, but is not limited thereto.
The embodiment of the invention also provides application of the bionic super-smooth surface based antifouling titanium alloy material in the field of marine antifouling.
By the preparation process, the method for preparing the bionic super-smooth surface on the surface of the titanium alloy substrate to reduce the biofouling of the surface of the titanium alloy comprises the steps of firstly preparing nano-hole or nano-tube structures with different shapes, diameters and depths on the surface of the titanium alloy by an anodic oxidation method, then chemically modifying the surface or the interior of the nano-structure, reducing the surface energy of the nano-structure by the chemical modification, enabling a lubricant to be more easily immersed into holes of the nano-structure, and finally injecting the lubricant. The attachment resistance experiment of bacteria proves that the attachment amount of bacteria on the surface of the titanium alloy can be obviously reduced by the bionic super-smooth surface, the remarkable attachment resistance effect of bacteria is achieved, and meanwhile, the nano structure and the used reagent of the bionic super-smooth surface are nontoxic to the bacteria, so that the preparation method of the bionic super-smooth surface is a green, environment-friendly, efficient and antifouling method and has wider application prospect in the field of marine antifouling.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are explained in further detail below with reference to the accompanying drawings and several preferred embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The process of preparing the bionic super-smooth surface on the surface of the titanium alloy in the embodiment is shown in fig. 1, and comprises anodic oxidation, chemical modification and lubricant injection, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And the mixed solution of NaF and 0.14M is used as electrolyte, 10V voltage is applied at 25 ℃ for anodic oxidation, and the mixed solution is taken out after 30min and dried at 80 ℃ for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorooctyltriethoxysilane is 0.25 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 3H at room temperature, and then drying for 1H at 120 ℃.
Injecting a lubricant: injecting 40 mu L of poly-perfluoromethyl isopropyl ether into the surface of each modified Ti-6Al-4V titanium alloy, and placing the titanium alloy in a vacuum drying oven for 10h to remove air in the nano structure. And then the mixture is placed for 5 hours in an inclined way at 20 degrees, and redundant lubricant is removed to obtain the SLIPS-10V bionic super-smooth surface.
In the embodiment, the nano-pore junction with uniform size is obtained on the surface of the titanium alloy by an anodic oxidation methodAs shown in FIGS. 2a and 2b, the diameter of the nano-pores is 20nm, the depth of the nano-pores is about 185nm, and the pore volume per square micron of the titanium alloy surface is calculated to be about 1.533X 10-2μm3。
Example 2
The process of preparing the bionic super-smooth surface on the surface of the titanium alloy in the embodiment is shown in fig. 1, and comprises anodic oxidation, chemical modification and lubricant injection, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And a mixed solution of 0.14M NaF is used as an electrolyte, 15V voltage is applied at 25 ℃ for anodic oxidation, and the anode is taken out after 30min and dried at 80 ℃ for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorooctyltriethoxysilane is 0.25 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 3H at room temperature, and then drying for 1H at 120 ℃.
Injecting a lubricant: injecting 40 mu L of poly-perfluoromethyl isopropyl ether into the surface of each modified Ti-6Al-4V titanium alloy, and placing the titanium alloy in a vacuum drying oven for 10h to remove air in the nano structure. And then the mixture is placed for 5 hours in an inclined way at 20 degrees, and redundant lubricant is removed to obtain the SLIPS-15V bionic super-smooth surface.
As the anodic oxidation voltage is increased, the nano-pore structure is transformed into the nano-tube structure, as shown in fig. 2c and fig. 2d, when the anodic oxidation voltage is 15V, the nano-tube structure with uniform size is obtained on the surface of the titanium alloy, the diameter of the nano-tube is 40nm, the depth of the nano-tube is about 250nm, and the calculated pore volume per square micron of the surface of the titanium alloy is about 3.7680 multiplied by 10-2μm3。
Example 3
The process of preparing the bionic super-smooth surface on the surface of the titanium alloy in the embodiment is shown in fig. 1, and comprises anodic oxidation, chemical modification and lubricant injection, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And 0.14M NaF is used as electrolyte, and the mixed solution is subjected to anodic oxidation by applying 30V voltage at 25 ℃, taken out after 30min and dried at 80 ℃ for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorooctyltriethoxysilane is 0.25 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 3H at room temperature, and then drying for 1H at 120 ℃.
Injecting a lubricant: injecting 40 mu L of poly-perfluoromethyl isopropyl ether into the surface of each modified Ti-6Al-4V titanium alloy, and placing the titanium alloy in a vacuum drying oven for 10h to remove air in the nano structure. And then the mixture is placed for 5 hours in an inclined way at 20 degrees, and redundant lubricant is removed to obtain the bionic super-smooth surface SLIPS-30V.
The size of the nanotubes further increased with the anodization voltage as shown in fig. 2e and 2f, the diameter of the nanotubes obtained on the surface of the titanium alloy was 100nm, the depth of the tubes was about 520nm, and the calculated pore volume per square micrometer of the titanium alloy surface was about 14.287 × 10 at an anodization voltage of 30V-2μm3。
Example 4
The bionic super-smooth surface prepared on the surface of the titanium alloy comprises anodic oxidation, chemical modification and lubricant injection, and the preparation method comprises the following specific steps:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: taking pretreated Ti-6Al-4V titanium alloy as an anode, a platinum sheet as a cathode and 1M H3PO4And a mixed solution of HF and 0.3M is used as an electrolyte, a voltage of 20V is applied at 15 ℃ for anodic oxidation, and the anode is taken out after 3min and dried at 80 ℃ for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorodecaalkyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorodecaalkyltriethoxysilane is 1 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 6H at room temperature, and then drying for 4H at 80 ℃.
Injecting a lubricant: injecting 40 mu L of poly-perfluoromethyl isopropyl ether into the surface of each modified Ti-6Al-4V titanium alloy, and placing the titanium alloy in a vacuum drying oven for 10h to remove air in the nano structure. And then the mixture is placed for 5 hours in an inclined way at 20 degrees, and redundant lubricant is removed to obtain the bionic super-smooth surface.
In this embodiment, the diameter of the nanotube obtained on the surface of the titanium alloy is 30nm, the depth of the nanotube is about 200nm, and the thickness of the nanostructure layer is 200 nm.
Example 5
The bionic super-smooth surface prepared on the surface of the titanium alloy comprises anodic oxidation, chemical modification and lubricant injection, and the preparation method comprises the following specific steps:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.1M H is taken3PO4Mixing with 0.03M NaF as electrolyte, anodizing at 35 deg.C under 5V for 60min, and cooling at 80 deg.CDrying the mixture for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorodecyl triethoxysilane is 0.01 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking at 60 ℃ for 24H, and then drying at 130 ℃ for 0.5H.
Injecting a lubricant: injecting 40 mu L of poly-perfluoromethyl isopropyl ether into the surface of each modified Ti-6Al-4V titanium alloy, and placing the titanium alloy in a vacuum drying oven for 10h to remove air in the nano structure. Then the mixture is placed for 5 hours with an inclination of 10 degrees, and the redundant lubricant is removed to obtain the bionic super-smooth surface.
The diameter of the nano-pores obtained on the surface of the titanium alloy in the embodiment is 10nm, the depth of the pores is about 50nm, and the thickness of the nano-structure layer is 50 nm.
Example 6
The bionic super-smooth surface prepared on the surface of the titanium alloy comprises anodic oxidation, chemical modification and lubricant injection, and the preparation method comprises the following specific steps:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.1M H is taken3PO4And the mixed solution of NaF and 0.03M is used as electrolyte, and the anode oxidation is carried out by applying 50V voltage at 25 ℃, and the anode is taken out after 30min and dried at 80 ℃ for standby.
Chemical modification: preparing ethanol solution of 1H,1H,2H, 2H-perfluorodecyl trichlorosilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorodecyl trichlorosilane is 0.01 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 1H at 20 ℃, and then drying for 0.5H at 130 ℃.
Injecting a lubricant: injecting 40 mu L of poly-perfluoromethyl isopropyl ether into the surface of each modified Ti-6Al-4V titanium alloy, and placing the titanium alloy in a vacuum drying oven for 10h to remove air in the nano structure. And then vertically placing for 1h, and removing the redundant lubricant to obtain the bionic super-smooth surface.
The diameter of the nanotube hole obtained on the surface of the titanium alloy in the embodiment is 200nm, the depth of the nanotube is about 600nm, and the thickness of the nanostructure layer is 600 nm.
Comparative example 1
The comparative example differs from example 1 in that: the steps of chemical modification and lubricant injection are lacked.
In the comparative example, only anodic oxidation treatment is carried out on the surface of the titanium alloy, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And the mixed solution of NaF and 0.14M is used as electrolyte, 10V voltage is applied at 25 ℃ for anodic oxidation, and the mixed solution is taken out after 30min and dried at 80 ℃ for later use.
Comparative example 2
The comparative example differs from example 1 in that: the step of lubricant injection is absent.
The treatment of the titanium alloy surface in the comparative example comprises anodic oxidation and chemical modification, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And 0.14M NaF as electrolyte, applying 10V voltage at 25 deg.C for anodizing, taking out after 30min, and coolingDrying at 80 ℃ for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorooctyltriethoxysilane is 0.25 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 3H at room temperature, and then drying for 1H at 120 ℃.
Comparative example 3
The comparative example differs from example 2 in that: the steps of chemical modification and lubricant injection are lacked.
In the comparative example, only anodic oxidation treatment is carried out on the surface of the titanium alloy, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And a mixed solution of 0.14M NaF is used as an electrolyte, 15V voltage is applied at 25 ℃ for anodic oxidation, and the anode is taken out after 30min and dried at 80 ℃ for later use.
Comparative example 4
The comparative example differs from example 2 in that: the step of lubricant injection is absent.
The treatment of the titanium alloy surface in the comparative example comprises anodic oxidation and chemical modification, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And 0.14M NaF as electrolyte, and applying 15V voltage at 25 deg.CAnodizing, taking out after 30min, and drying at 80 ℃ for later use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorooctyltriethoxysilane is 0.25 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 3H at room temperature, and then drying for 1H at 120 ℃.
Comparative example 5
The comparative example differs from example 3 in that: the steps of chemical modification and lubricant injection are lacked.
In the comparative example, only anodic oxidation treatment is carried out on the surface of the titanium alloy, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And 0.14M NaF is used as electrolyte, and the mixed solution is subjected to anodic oxidation by applying 30V voltage at 25 ℃, taken out after 30min and dried at 80 ℃ for later use.
Comparative example 6
The comparative example differs from example 3 in that: the step of lubricant injection is absent.
The treatment of the titanium alloy surface in the comparative example comprises anodic oxidation and chemical modification, and the specific preparation steps are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.5M H is taken3PO4And 0.14M NaFApplying 30V voltage as electrolyte at 25 deg.C for anodizing, taking out after 30min, and oven drying at 80 deg.C for use.
Chemical modification: preparing an ethanol solution of 1H,1H,2H, 2H-perfluorooctyltriethoxysilane as a modifying solution, wherein the concentration of the 1H,1H,2H, 2H-perfluorooctyltriethoxysilane is 0.25 vol%, immersing the anodized Ti-6Al-4V titanium alloy into the modifying solution, soaking for 3H at room temperature, and then drying for 1H at 120 ℃.
Comparative example 7
The comparative example differs from example 1 in that: the specific preparation steps for carrying out anodic oxidation treatment on the surface of the titanium alloy are as follows:
pretreatment of the titanium sheet: ti-6Al-4V titanium alloy with the thickness of 30 multiplied by 20 multiplied by 3mm is taken as a matrix, SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes, 2000 meshes and 3000 meshes is adopted to polish the titanium alloy, and then the titanium alloy is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Anodic oxidation method for preparing TiO2Nano-structure: pretreated Ti-6Al-4V titanium alloy is taken as an anode, a platinum sheet is taken as a cathode, and 0.65 wt.% of NH is added4And (3) taking a glycerol-water mixed solution of the F (the volume ratio of glycerol to water is 3:1) as an electrolyte, applying 60V voltage at 40 ℃ for anodic oxidation, taking out after 2h, and drying at 80 ℃ for later use.
As can be seen from the scanning electron micrograph (fig. 2g), the nanostructure layer obtained in comparative example 7 includes both nanopores and nanotubes, the size of the nanopores is about 30nm, and the size of the nanotubes is about 100 nm. However, the surface of the nano structure is covered with a layer of chips, so that the flatness is poor, the size is not uniform, and the anodic oxidation for preparing the nano structure has higher voltage and longer time.
FIG. 3 is a Raman spectrum of the titanium alloy material after the anodic oxidation obtained in examples 1, 2 and 3 of the present invention. In FIG. 3, the Raman spectra of the anodized titanium alloy are at 141, 233, 443, 619cm-1The peak of rutile appears, which indicates that the composition of the nanopore and the nanotube is rutile type titanium dioxide, and the rutile type nanometer titanium dioxide has no bactericidal property according to the literature report.
Fig. 4a and 4b are schematic diagrams illustrating changes of contact angle, rolling angle and rolling speed of the titanium alloy material (SLIPS-10V, SLIPS-15V, SLIPS-30V) with the bionic super-smooth surface obtained in example 1, example 2 and example 3 of the invention in an escherichia coli solution for soaking for different times. As can be seen from FIGS. 4a and 4b, the rolling angle was about 2 ℃ and the sliding speed was about 1mm/s before the three titanium alloys with lubricant were immersed in the E.coli solution, indicating that the surface had an ultra-smooth property which prevented the contaminants from contacting the substrate and the contaminants were easily carried away by water. Along with the prolonging of the soaking time, the lubricant is lost, the contact angle and the rolling speed of the three bionic super-smooth surfaces are reduced, and the rolling angle is increased. When soaked in an escherichia coli solution for 5 days, the lubricant in the nanopore is greatly lost, the contact angle of SLIPS-10V is reduced to 107 degrees, and a water drop is difficult to roll on the substrate. The nanotubes with the largest diameter and depth have better stability in water because they can store more lubricant and have the property of slowly releasing the lubricant. After being soaked in the solution of the escherichia coli for 10 days, the contact angle is about 115 degrees, the sliding angle is less than 10 degrees, and the sliding speed is about 0.302 mm/s.
The colony patterns of the titanium alloy with the bionic super-smooth surface obtained in the examples 1 to 3 of the invention and the titanium alloy treated in the comparative examples 1 to 6 after being soaked in the escherichia coli solution for 1 day are shown in fig. 5a and 5b, the colony patterns after 5 days are shown in fig. 5c and 5d, and the colony patterns after 10 days are shown in fig. 5e and 5 f. As can be seen from fig. 5 a-5 f, when the titanium alloy is soaked in the escherichia coli solution for one day, the adhesion amounts of the surfaces of the anodized titanium alloy and the chemically modified titanium alloy of the escherichia coli are large, and the adhesion amounts of different samples are not obviously different, which indicates that the adhesion prevention behavior of the escherichia coli is slightly affected by the nanostructure and the chemical modification, but after the lubricant is injected, the surface of the titanium alloy has almost no bacterial colony, indicating that the adhesion amount of the escherichia coli can be reduced due to the ultra-slip property of the lubricant layer. The incubation was continued in the E.coli solution and the colony count started to increase due to loss of the lubricant. Among them, the colony count of the titanium alloy with the biomimetic ultra-smooth surface obtained in example 1 is increased most because of the loss of a large amount of the lubricant in the nanopore, while the colony count of the titanium alloy with the biomimetic ultra-smooth surface obtained in example 3 is still very small, which is consistent with the small rolling angle and the large rolling speed. The large-size nanotube structure can store more lubricant and has a slow release effect, so that the long-term antifouling effect is achieved.
In addition, the inventor also refers to the modes of examples 1-6, tests are carried out by using other raw materials and conditions listed in the specification, and the antifouling titanium alloy material based on the bionic super-smooth surface, which can obviously reduce the attachment amount of bacteria on the titanium alloy surface, has a remarkable antibacterial attachment effect, has an excellent slow release effect and the like, is also prepared.
It should be understood that the above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. All the technical solutions formed by equivalent transformation or equivalent replacement fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of an antifouling titanium alloy material based on a bionic super-smooth surface is characterized by comprising the following steps:
providing a titanium alloy substrate;
processing the titanium alloy substrate by adopting an anodic oxidation method, and forming a nanostructure layer arranged in an array on the surface of the titanium alloy substrate, wherein the nanostructure layer comprises nanopores or nanotubes, the diameter of each nanopore is 10-30 nm, the depth of each nanopore is 50-200 nm, the diameter of each nanotube is 30-200 nm, and the depth of each nanotube is 200-600 nm;
chemically modifying the titanium alloy substrate with the nanostructure layer by using a fluorosilane modifier;
and applying a lubricant to the surface of the chemically modified titanium alloy substrate to obtain the antifouling titanium alloy material based on the bionic super-smooth surface.
2. The production method according to claim 1, characterized by comprising: performing anodic oxidation by using a constant-voltage direct-current power supply and a titanium alloy substrate as an anode to form a nanostructure layer on the surface of the titanium alloy substrate; preferably, the material of the nanostructure layer comprises rutile titanium dioxide; and/or the thickness of the nanostructure layer is 50-600 nm.
3. The production method according to claim 1 or 2, wherein the anodic oxidation method employs process conditions including: the voltage is 5-50V, the electrolyte comprises a mixed solution of acid and fluoride, the temperature of anodic oxidation is 15-35 ℃, and the time of anodic oxidation is 3-60 min; preferably, the acid comprises phosphoric acid and/or sulfuric acid; preferably, the concentration of phosphoric acid or sulfuric acid in the mixed solution is 0.1-1.0M, and preferably, the fluoride comprises any one or a combination of more than two of ammonium fluoride, sodium fluoride and hydrofluoric acid; preferably, the concentration of the fluoride in the mixed solution is 0.03-0.30M.
4. The method of claim 1, wherein: the fluorosilane modifier comprises any one or the combination of more than two of 1H,1H,2H, 2H-perfluorodecaalkyltriethoxysilane, 1H,2H, 2H-perfluorodecyltriethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane, 1H,2H, 2H-perfluorodecyltrichlorosilane and heptadecafluorodecyltrimethoxysilane; and/or the concentration of the fluorosilane modifier in the fluorosilane modifying solution is 0.01-1 vol%; preferably, the fluorosilane modifying solution comprises a mixed solution of a fluorosilane modifying agent and ethanol.
5. The method of claim 1, wherein: the temperature of the chemical modification is 20-60 ℃, and the time is 1-24 h; and/or, the preparation method further comprises the following steps: and drying the chemically modified titanium alloy substrate, wherein the drying temperature is 80-130 ℃, and the time is 0.5-4 h.
6. The method of claim 1, wherein: the lubricant comprises one or two of Krytox perfluorooil, perfluoropolyether, silicone oil and ionic liquidCombinations of the above; and/or the application amount of the lubricant is 1-10 mu L/cm2。
7. The method of claim 1, further comprising: applying a lubricant to the surface of the chemically modified titanium alloy substrate, injecting at least part of the lubricant into the nanostructure layer, drying to remove gas in the nanostructure layer, and then obliquely placing to remove the redundant lubricant; preferably, the inclination angle is 10-90 degrees.
8. An antifouling titanium alloy material based on a biomimetic ultra-smooth surface prepared by the method of any of claims 1-7.
9. The antifouling titanium alloy material based on the bionic super-smooth surface is characterized by comprising a titanium alloy substrate and the bionic super-smooth surface arranged on the surface of the titanium alloy substrate, wherein the bionic super-smooth surface comprises a nano-structure layer, a low surface energy substance modified on the surface and/or inside the nano-structure layer and a lubricant distributed on the surface and inside the nano-structure layer;
preferably, the contact angle between the antifouling titanium alloy material based on the bionic super-smooth surface and water is 115-125 degrees, the rolling angle is 2-5 degrees, and the sliding speed is 0.8-1.5 mm/s;
preferably, after the antifouling titanium alloy material based on the bionic super-smooth surface is soaked in an escherichia coli solution for 10 days, the contact angle of the antifouling titanium alloy material with water is 90-120 degrees, the rolling angle is 4-50 degrees, and the sliding speed is 0.01-0.4 mm/s;
preferably, after the antifouling titanium alloy material based on the bionic super-smooth surface is soaked in an escherichia coli solution for 10 days, the attachment amount of escherichia coli on the surface is less than 32000 CFU/ml;
preferably, the thickness of the nanostructure layer is 50-600 nm; preferably, the nanostructure layer comprises nanopores or nanotubes, wherein the diameter of the nanopores is 10-30 nm, the depth of the nanopores is 50-200 nm, the diameter of the nanotubes is 30-200 nm, and the depth of the nanotubes is 200-600 nm; preferably, the material of the nanostructure layer comprises rutile titanium dioxide; preferably, the low surface energy substance is derived from a fluorosilane modifier, and the fluorosilane modifier comprises any one or a combination of more than two of 1H,1H,2H, 2H-perfluorodecaalkyltriethoxysilane, 1H,2H, 2H-perfluorodecyltriethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane, 1H,2H, 2H-perfluorodecyltrichlorosilane and heptadecafluorodecyltrimethoxysilane;
preferably, the lubricant comprises any one or a combination of more than two of Krytox perfluorooil, perfluoropolyether, silicone oil and ionic liquid.
10. Use of the biomimetic ultra-smooth surface based antifouling titanium alloy material according to claim 8 or 9 in the field of marine antifouling.
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| CN111958076A (en) * | 2020-07-11 | 2020-11-20 | 吉林大学 | Bionic metal laminated plate with self-cleaning function and preparation method thereof |
| CN112813392A (en) * | 2020-12-31 | 2021-05-18 | 中国科学院宁波材料技术与工程研究所 | Solid-liquid compound wear-resistant antibacterial material based on capillary action, preparation method and application |
| CN113403661A (en) * | 2021-06-17 | 2021-09-17 | 中国计量大学 | Preparation method and application of titanium alloy anodic oxidation super-hydrophobic coating |
| CN113481564A (en) * | 2021-06-30 | 2021-10-08 | 中国科学院金属研究所 | Titanium-based alloy with bionic super-smooth surface structure and preparation method and application thereof |
| CN113737247A (en) * | 2021-09-28 | 2021-12-03 | 湖南大学 | Sliding surface, preparation method and application thereof |
| CN114955984A (en) * | 2022-05-18 | 2022-08-30 | 深圳技术大学 | Method for manufacturing ultra-smooth surface and micro-fluidic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111958076A (en) * | 2020-07-11 | 2020-11-20 | 吉林大学 | Bionic metal laminated plate with self-cleaning function and preparation method thereof |
| CN112813392A (en) * | 2020-12-31 | 2021-05-18 | 中国科学院宁波材料技术与工程研究所 | Solid-liquid compound wear-resistant antibacterial material based on capillary action, preparation method and application |
| CN113403661A (en) * | 2021-06-17 | 2021-09-17 | 中国计量大学 | Preparation method and application of titanium alloy anodic oxidation super-hydrophobic coating |
| CN113481564A (en) * | 2021-06-30 | 2021-10-08 | 中国科学院金属研究所 | Titanium-based alloy with bionic super-smooth surface structure and preparation method and application thereof |
| CN113737247A (en) * | 2021-09-28 | 2021-12-03 | 湖南大学 | Sliding surface, preparation method and application thereof |
| CN114955984A (en) * | 2022-05-18 | 2022-08-30 | 深圳技术大学 | Method for manufacturing ultra-smooth surface and micro-fluidic device |
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