CN114369277B - Super-hydrophilic surface with high aspect ratio micro/nano composite structure and preparation method thereof - Google Patents
Super-hydrophilic surface with high aspect ratio micro/nano composite structure and preparation method thereof Download PDFInfo
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- CN114369277B CN114369277B CN202111098055.7A CN202111098055A CN114369277B CN 114369277 B CN114369277 B CN 114369277B CN 202111098055 A CN202111098055 A CN 202111098055A CN 114369277 B CN114369277 B CN 114369277B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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Abstract
A super-hydrophilic surface with a micro/nano composite structure with a high aspect ratio and a preparation method thereof are disclosed, wherein the micro/nano composite structure with the high aspect ratio is grafted on the surface of high cross-linked polyethylene, the micro-scale structure is formed by alternately combining poly-2-methacryloyloxyethyl phosphorylcholine cylinders and square columns, and the nano-scale structure is a 2-methacryloyloxyethyl phosphorylcholine molecular brush. The high aspect ratio micro-nano composite structure adopted by the invention can improve the surface hydrophilicity to a great extent, realize the crossing from hydrophilicity to super hydrophilicity and widen the application range of the high cross-linked polyethylene.
Description
Technical Field
The invention relates to the technical field of processing a super-hydrophilic micro-nano composite pattern structure, in particular to a preparation method of a super-hydrophilic surface with a cross-scale high depth-to-width ratio micro-nano composite pattern structure.
Background
The hydrophilic surface formed by grafting 2-methacryloyloxyethyl phosphorylcholine on the surface of high-crosslinked polyethylene is widely applied to the field of artificial joints, and the 2-methacryloyloxyethyl phosphorylcholine is also widely applied to vascular stents, contact lenses and the like due to the excellent hydrophilic performance, but the super-hydrophilicity cannot be realized by only using the hydrophilic surface formed by grafting and polymerizing the 2-methacryloyloxyethyl phosphorylcholine, and the requirements of partial fields cannot be met. Therefore, it is of unusual interest to study surfaces with ultra-hydrophilic properties.
In recent years, methods for improving the surface hydrophilic property of the material mainly include surface grafting modification, plasma implantation modification and surface patterning treatment, however, the hydrophilic property of the material surface improved by the methods often cannot meet the expected requirement.
Researches find that 2-methacryloyloxyethyl phosphorylcholine and a cross-linking agent N, N '-methylene bisacrylamide can form a three-dimensional network structure under the ultraviolet irradiation condition, and the unique structure enables the cross-linking agent N, N' -methylene bisacrylamide to have excellent hydrophilic performance.
Disclosure of Invention
A superhydrophilic surface having a high aspect ratio micro/nano composite structure, characterized by: assembling a hydrophilic micro/nano composite structure on the surface of high cross-linked polyethylene (HXLPE) to obtain a super-hydrophilic surface with a micro/nano composite structure with a high aspect ratio; the micro/nano composite structure is formed by grafting and polymerizing a hydrophilic monomer 2-Methacryloyloxyethyl Phosphorylcholine (MPC) under the induction of ultraviolet irradiation and mutually crosslinking under the action of a crosslinking agent N, N' -Methylene Bisacrylamide (MBA); in the micro/nano composite structure, a micron-scale structure is formed by alternately combining a cylinder and a square column, the height of the micron-scale structure is 300 to 500 mu m, the diameter of the cylinder structure is 20 to 30 mu m, the side length of the square column structure is 20 to 30 mu m, the distance between the structures is 20 to 30 mu m, the nano-scale structure is a 2-Methacryloyloxyethyl Phosphorylcholine (MPC) molecular brush, and the scale is 1 to 100 nm; the high aspect ratio is that the aspect ratio of the micro/nano composite structure is 10 to 1.
A method for preparing a super-hydrophilic surface with a micro/nano composite structure with a high aspect ratio is characterized by mainly comprising the following steps:
(1) Grinding and polishing the surface of a high-crosslinking polyethylene test piece, sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water, and drying to obtain a smooth high-crosslinking polyethylene surface;
(2) Selecting a metal silver sheet as a pattern template, grinding and polishing the silver sheet to obtain a smooth silver sheet, and processing regularly arranged circular holes and square holes on the surface of the smooth silver sheet by adopting one or two processing modes of laser processing and photoetching technology to obtain the silver sheet with a combined pattern penetrating through the circular holes and the square holes;
(3) Covering a smooth high-crosslinking polyethylene surface with a silver sheet with a combined pattern of a through circular hole and a square hole, immersing the silver sheet and the smooth high-crosslinking polyethylene surface into an acetone solution of benzophenone, and drying in a dark room to obtain a combined test piece with the surface attached with the benzophenone;
(4) Dissolving 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and N, N '-Methylene Bisacrylamide (MBA) in degassed pure water, uniformly stirring, introducing argon into a closed container to remove oxygen, and obtaining a mixed solution of 2-methacryloyloxyethyl phosphorylcholine solution/N, N' -methylene bisacrylamide;
(5) The method comprises the following steps of immersing a combined test piece with benzophenone attached to the surface in a mixed solution of 2-methacryloyloxyethyl phosphorylcholine solution/N, N '-methylene bisacrylamide, and then carrying out continuous irradiation of ultraviolet light in a dark room, wherein the ultraviolet light cannot penetrate through a silver sheet, so that a hydrophilic monomer 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) can be induced to carry out graft polymerization only at a combined pattern of a circular hole and a square hole of the silver sheet, and a poly 2-Methacryloyloxyethyl Phosphorylcholine (MPC) composite structure with the shape consistent with that of the combined pattern of the circular hole and the square hole is formed;
(6) After irradiation, removing the silver sheet which is covered on the smooth high-crosslinking polyethylene surface and has a combined pattern of a through circular hole and a square hole, sequentially carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water, and drying to obtain the super-hydrophilic surface with a micro/nano composite structure with a high aspect ratio, wherein the contact angle of water drops on the surface is less than 4 degrees.
The surface roughness Ra of the high crosslinking polyethylene surface in the step (1) is less than 0.1 μm.
The smooth silver sheet in the step (2) has the surface roughness Ra of less than 0.1 μm and the thickness of 400 μm-500 μm, so that the thickness of the micro/nano composite structure can be adjusted within the range of 500 μm.
The diameter of the circular hole is 20 to 30 mu m, the side length of the square hole is 20 to 30 mu m, and the hole pitch is 20 to 30 mu m.
And (4) immersing the benzophenone in the acetone solution of the benzophenone in the step (3) for 15 to 20min at the temperature of 20 to 25 ℃ and the relative humidity of 30 to 35%, wherein the concentration of the benzophenone is 10 to 15 mg/mL.
The concentration of the 2-Methacryloyloxyethyl Phosphorylcholine (MPC) in the step (4) is 0.4 to 0.5mol/L, and the concentration of N, N' -Methylenebisacrylamide (MBA) is 0.2 to 0.25 mol/L.
The continuous ultraviolet irradiation condition in the step (5) is a 400W high-pressure mercury lamp, and the irradiation intensity is 5 to 8mw/cm 2 The irradiation distance is 20 to 25cm, and the irradiation time is 90 to 120min.
And (5) the darkroom is provided with a water cooling device, an ultraviolet light intensity meter and a thermometer, so that the influence caused by irradiation temperature rise can be controlled in time.
Drawings
FIG. 1 is a schematic view of a silver sheet with a combination of through holes and square holes
FIG. 2 is a schematic view of a composite test piece
FIG. 3 is a schematic diagram of a super-hydrophilic surface with a high aspect ratio micro/nano composite structure
FIG. 4 is a schematic diagram of deionized water droplets on a superhydrophilic surface with a high aspect ratio micro/nano composite structure
FIG. 5 is a schematic view of an ultraviolet light reaction apparatus
Detailed description of the preferred embodiments
A preparation method of a super-hydrophilic surface with a high aspect ratio micro/nano composite structure is sequentially carried out according to the following steps:
(1) Grinding and polishing the surface of the high cross-linked polyethylene, respectively carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water, and then carrying out drying treatment to obtain the surface of the high cross-linked polyethylene with the roughness Ra of less than 0.1 mu m;
(2) Selecting a metal silver sheet with the thickness of 500 mu m as a pattern template, grinding and polishing the silver sheet to obtain a smooth silver sheet, and processing regularly arranged circular holes and square holes on the surface of the smooth silver sheet by adopting one or two processing modes of laser processing and photoetching technology to obtain the silver sheet with a combined pattern penetrating through the circular holes and the square holes, wherein the diameter of the circular holes is 20 to 30 mu m, the side length of the square holes is 20 to 30 mu m, and the hole spacing is 20 to 30 mu m;
(3) Fixing a silver sheet with a combined pattern of a through round hole and a square hole on the surface of smooth high-crosslinking polyethylene, soaking the silver sheet into 15mg/mL acetone solution of benzophenone for 20min, and then drying the silver sheet in a dark room to obtain a combined test piece with the surface attached with the benzophenone;
(4) Dissolving 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and N, N ' -Methylene Bisacrylamide (MBA) in degassed pure water, uniformly stirring, introducing argon into a closed container to remove oxygen, and obtaining a mixed solution of 2-methacryloyloxyethyl phosphorylcholine solution/N, N ' -methylene bisacrylamide, wherein the concentration of the 2-Methacryloyloxyethyl Phosphorylcholine (MPC) is 0.4mol/L, and the concentration of the N, N ' -Methylene Bisacrylamide (MBA) is 0.2mol/L;
(5) Immersing the combined test piece with the surface adhered with the benzophenone in a mixed solution of 2-methylacryloyl ethyl acyloxy phosphoryl choline solution/N, N' -methylene-bisacrylamide, and feeding the mixed solution by using a double-layer polypropylene filmSealing, continuously irradiating with ultraviolet lamp in dark room for 100min, introducing cooling water in the dark room during irradiation, wherein the ultraviolet lamp is 400W high-pressure mercury lamp, and the irradiation intensity is 5mw/cm 2 And the irradiation distance is 20cm, and the hydrophilic monomer 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) are induced to perform graft polymerization at the combined pattern of the circular hole and the square hole of the silver sheet to form a poly 2-Methacryloyloxyethyl Phosphorylcholine (MPC) composite structure with the shape consistent with that of the combined pattern of the circular hole and the square hole.
(6) And after the irradiation is finished, removing the silver sheet with the combined pattern of the through circular holes and the square holes, sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water, and drying to obtain the super-hydrophilic surface with the high aspect ratio micro/nano composite structure.
The super-hydrophilic surface prepared by the preparation method of the super-hydrophilic surface with the micro/nano composite structure with the high aspect ratio in the embodiment is subjected to water contact angle measurement by using deionized water drops, 10 points on the surface are measured, the average value of the 10 points is taken, and the water contact angle is stabilized at 2 degrees. The analysis and test result shows that: the super-hydrophilic surface preparation method with the high aspect ratio micro/nano composite structure can realize the super-hydrophilic performance of the surface.
Claims (9)
1. A superhydrophilic surface having a high aspect ratio micro/nano composite structure, characterized by: assembling a hydrophilic micro/nano composite structure on the surface of high cross-linked polyethylene (HXLPE) to obtain a super-hydrophilic surface with a micro/nano composite structure with a high aspect ratio; the micro/nano composite structure is formed by grafting and polymerizing a hydrophilic monomer 2-Methacryloyloxyethyl Phosphorylcholine (MPC) under the induction of ultraviolet irradiation and mutually crosslinking under the action of a crosslinking agent N, N' -Methylene Bisacrylamide (MBA); in the micro/nano composite structure, a micron-scale structure is formed by alternately combining cylinders and square columns, the height of the micron-scale structure is 300-500 mu m, the diameter of a cylinder structure is 20-30 mu m, the side length of the square column structure is 20-30 mu m, the distance between the structures is 20-30 mu m, a nano-scale structure is a 2-Methacryloyloxyethyl Phosphorylcholine (MPC) molecular brush, and the scale is 1-100 nm; the high aspect ratio is that the aspect ratio of the micro/nano composite structure is 10 to 1.
2. A method for preparing the superhydrophilic surface with high aspect ratio micro/nano composite structure as defined in claim 1, which mainly comprises the following steps:
(1) Grinding and polishing the surface of a high-crosslinking polyethylene test piece, sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water, and drying to obtain a smooth high-crosslinking polyethylene surface;
(2) Selecting a metal silver sheet as a pattern template, grinding and polishing the silver sheet to obtain a smooth silver sheet, and processing regularly arranged circular holes and square holes on the surface of the smooth silver sheet by adopting one or two processing modes of laser processing and photoetching technology to obtain the silver sheet with a combined pattern penetrating through the circular holes and the square holes;
(3) Covering a smooth high-crosslinking polyethylene surface with a silver sheet with a combined pattern of a through circular hole and a square hole, immersing the silver sheet and the smooth high-crosslinking polyethylene surface into an acetone solution of benzophenone, and drying in a dark room to obtain a combined test piece with the surface attached with the benzophenone;
(4) Dissolving 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and N, N '-Methylene Bisacrylamide (MBA) in degassed pure water, uniformly stirring, introducing argon into a closed container to remove oxygen, and obtaining a mixed solution of 2-methacryloyloxyethyl phosphorylcholine solution/N, N' -methylene bisacrylamide;
(5) The method comprises the following steps of immersing a combined test piece with benzophenone attached to the surface in a mixed solution of 2-methacryloyloxyethyl phosphorylcholine solution/N, N '-methylene bisacrylamide, and then carrying out continuous irradiation of ultraviolet light in a dark room, wherein the ultraviolet light cannot penetrate through a silver sheet, so that a hydrophilic monomer 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) can be induced to carry out graft polymerization only at a combined pattern of a circular hole and a square hole of the silver sheet, and a poly 2-Methacryloyloxyethyl Phosphorylcholine (MPC) composite structure with the shape consistent with that of the combined pattern of the circular hole and the square hole is formed;
(6) After irradiation, removing the silver sheet which is covered on the smooth high-crosslinking polyethylene surface and has a combined pattern of a through circular hole and a square hole, sequentially carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water, and drying to obtain the super-hydrophilic surface with a micro/nano composite structure with a high aspect ratio, wherein the contact angle of water drops on the surface is less than 4 degrees.
3. The method of claim 2, wherein the method comprises the steps of: the surface roughness Ra of the high crosslinking polyethylene surface in the step (1) is less than 0.1 μm.
4. The method of claim 2, wherein the method comprises the steps of: the smooth silver sheet in the step (2) has the surface roughness Ra of less than 0.1 μm and the thickness of 500 μm, so that the height of the micro/nano composite structure is adjusted within the range of 500 μm.
5. The method of claim 2, wherein the method comprises the steps of: the diameter of the circular hole and the diameter of the square hole which are regularly arranged in the step (2) are 20 to 30 micrometers, the side length of the square hole is 20 to 30 micrometers, and the hole distance is 20 to 30 micrometers.
6. The method of claim 2, wherein the method comprises the steps of: and (3) immersing the benzophenone in the acetone solution of the benzophenone in the step (3) for 15 to 20min at the temperature of 20 to 25 ℃ and the relative humidity of 30 to 35%, wherein the concentration of the benzophenone is 10 to 15 mg/mL.
7. The method of claim 2, wherein the method comprises the steps of: the concentration of the 2-Methacryloyloxyethyl Phosphorylcholine (MPC) in the step (4) is 0.4 to 0.5mol/L, and the concentration of the N, N' -Methylenebisacrylamide (MBA) is 0.2 to 0.25 mol/L.
8. The method of claim 2, wherein the method comprises the steps of: the continuous ultraviolet irradiation condition in the step (5) is a 400W high-pressure mercury lamp, and the irradiation intensity is 5 to 8mw/cm 2 The irradiation distance is 20 to 25cm, and the irradiation time is 90 to 120min.
9. The method of claim 2, wherein the method comprises the steps of: and (5) arranging a water cooling device, an ultraviolet light intensity meter and a thermometer in the darkroom to control the influence caused by irradiation temperature rise in time.
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| CN102078227A (en) * | 2010-11-24 | 2011-06-01 | 南京理工大学 | Polyethylene artificial joint capable of improving biocompatibility and tribological property and preparation method thereof |
| CN102492950A (en) * | 2011-12-16 | 2012-06-13 | 南京理工大学 | Bionic multi-scale structural surface with excellent tribological performance and preparation method |
| CN105169490B (en) * | 2015-09-28 | 2018-09-25 | 南京理工大学 | A kind of low friction polyether-ether-ketone joint prosthesis mortar and preparation method thereof |
| CN108043246B (en) * | 2017-12-14 | 2021-06-04 | 北京林业大学 | Preparation method of super-hydrophilic organic membrane based on micro-nano structure surface imprinting |
| CN113350570B (en) * | 2021-06-17 | 2022-03-08 | 湘潭大学 | Artificial joint with self-repairing textured composite film structure and preparation method thereof |
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