CN113481564A - Titanium-based alloy with bionic super-smooth surface structure and preparation method and application thereof - Google Patents
Titanium-based alloy with bionic super-smooth surface structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a titanium-based alloy with a bionic super-smooth surface structure, a preparation method and application thereof, wherein the bionic super-smooth surface structure comprises a two-stage rough surface structure and a lubricant layer; wherein, the two-stage rough surface structure is formed by compounding a concave-convex macroscopic structure and a porous microscopic structure; the lubricant layer covers the two-stage rough surface structure. The preparation method of the titanium-based alloy with the bionic super-smooth surface structure mainly comprises the steps of pretreatment, concave-convex macroscopic structure processing, porous microstructure preparation and post-treatment. The invention is mainly used for constructing and preparing the bionic super-smooth surface structure on the titanium-based alloy, the bionic super-smooth surface structure is easy to prepare, has good friction resistance, larger oil storage capacity and lower lubricant dissipation rate, and has important guiding significance for improving the biological adhesion resistance of the titanium-based alloy and expanding the application potential of the titanium-based alloy in the biological fouling resistance field of ships, ocean engineering, medical instruments and the like.
Description
Technical Field
The invention relates to the technical field of anti-biological fouling materials, in particular to a titanium-based alloy with a bionic super-smooth surface structure, and a preparation method and application thereof.
Background
The titanium-based alloy is formed by adding other elements into titanium element serving as a base material, has the outstanding advantages of small density, high specific strength, good corrosion resistance, good impact resistance and the like, and is widely applied to the fields of chemical industry, aerospace, ships, ocean engineering, medical appliances and the like.
The titanium-based alloy has good biocompatibility, so that organisms with the adhesive capacity are easy to deposit and attach on the surface of the titanium-based alloy, biological fouling is caused, and a series of hazards are generated, such as increase of navigation resistance in shipping, slowing of navigation speed and increase of fuel consumption; pipelines are blocked in underwater pipeline transmission, so that the pipeline transportation efficiency is reduced, the service life is shortened and the like; in the field of medical devices, the surface adhesion of microorganisms such as bacteria can increase the infection risk of patients and induce serious problems such as postoperative infection. Therefore, improving the anti-biological fouling capability of the titanium-based alloy surface becomes one of the key problems for expanding the application of the titanium-based alloy surface in the fields of ships, ocean engineering, medical instruments and the like.
In recent years, inspired by the fact that microscopic halenia nepalensis has a thin mucus layer covering the cage mouth of halenia nepalensis in nature and has excellent anti-adhesion performance, a novel surface anti-adhesion technical method is provided, namely, smooth liquid is injected into a porous surface (also called bionic super-smooth surface), and the method is widely concerned in the field of anti-pollution. The bionic super-smooth surface has a plurality of excellent performances, such as corrosion prevention, icing prevention and self cleaning, and especially can prevent the attachment of protein or microorganism. For example, the prior art provides a method for preventing metal atmospheric corrosion by using an artificial imitation nepenthes super-smooth surface, and the main design idea is to construct a bionic super-smooth surface on a metal aluminum surface. However, the inventor of the present invention finds that the porous microstructure constructed by the anodic oxidation method is relatively fragile, the limited micro porous structure has small oil storage capacity, and the performance requirement of the long-term service of the material surface cannot be met. Therefore, the research and design of a new structure of the bionic super-smooth surface of the titanium-based alloy, which is resistant to abrasion, large in oil storage capacity and low in lubricant dissipation rate, has important significance in improving the application of the bionic super-smooth surface of the titanium-based alloy in the fields of biological fouling resistance of ships, ocean engineering, medical instruments and the like.
Disclosure of Invention
In view of the above, the invention provides a titanium-based alloy with a bionic super-smooth surface structure, and a preparation method and application thereof, and mainly aims to construct the bionic super-smooth surface structure which is good in anti-friction capability, large in oil storage capacity and low in lubricant dissipation rate on the titanium-based alloy.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a titanium-based alloy with a biomimetic ultra-smooth surface structure, where the biomimetic ultra-smooth surface structure includes:
the two-stage rough surface structure is formed by compounding a concave-convex macroscopic structure and a porous microscopic structure;
a lubricant layer overlying the two-stage rough surface structure;
and the two-stage rough surface structure and the lubricant layer are compounded to form the bionic super-smooth surface structure of the titanium-based alloy.
Preferably, the two-stage rough surface structure is grafted with a fluorinated polymer, so that the lubricant layer is covered on the two-stage rough surface structure under the action of the fluorinated polymer; preferably, the fluorinated polymer is perfluorooctyltriethoxysilane or 1,1,2, 2-perfluorodimethylcyclohexane.
Preferably, the lubricant in the lubricant layer is perfluoropolyether or polydimethylsiloxane.
Preferably, the lubricant in the lubricant layer is in a viscous state, and further preferably, the viscosity of the lubricant is in a range of 5 to 250cSt at 40 ℃.
Preferably, the lubricant layer has a thickness of 10 to 100 μm.
Preferably, the relief macrostructures comprise a predetermined array pattern; the preset array pattern is formed by arranging a plurality of regular polygon patterns; wherein the convex portions of the concavo-convex macrostructures correspond to line portions (i.e., sides of regular polygons) on the regular polygonal patterns, and the concave portions of the concavo-convex macrostructures correspond to portions other than the line portions in each of the patterns;
preferably, the depth of the concave part is 30-300 μm;
preferably, the diameter of the inscribed circle of the regular polygon is 0.3-1.5 mm;
preferably, the predetermined array pattern includes one or more shapes of regular polygon patterns.
Preferably, in the predetermined array pattern, each regular polygon has a common edge with its adjacent regular polygon.
Preferably, the porous microstructure has a pore diameter of 20 to 150nm and a pore depth of 0.2 to 10 μm.
On the other hand, the embodiment of the invention provides a preparation method of a titanium-based alloy with a bionic super-smooth surface structure, which comprises the following steps:
processing a concave-convex macrostructure: processing a concave-convex macro structure on the surface of the titanium-based alloy;
preparing a porous microstructure: carrying out anodic oxidation treatment on the titanium-based alloy treated by the step of processing the concave-convex macrostructure, and preparing a porous microstructure on the surface of the titanium-based alloy;
post-treatment: and sequentially carrying out surface chemical modification treatment and lubricant impregnation treatment on the titanium-based alloy treated by the step of preparing the porous microstructure to obtain the titanium-based alloy with the bionic super-smooth surface structure.
Preferably, in the step of processing the concavo-convex macrostructure: processing a concave-convex macro structure on the surface of the titanium-based alloy by a physical method; preferably, the physical method comprises one or more of machining, screen printing etching and laser processing.
Preferably, before the step of processing the concave-convex macrostructure, the method further comprises a pretreatment step; wherein the pretreatment step comprises: and cleaning and drying the titanium-based alloy.
Preferably, in the step of preparing the porous microstructure: taking the titanium-based alloy treated by the step of processing the concave-convex macroscopic structure as an anode, and taking a graphite sheet or a platinum sheet as a cathode; inserting an anode and a cathode into the electrolyte, applying direct current voltage to carry out electrolysis, and preparing a porous microstructure on the surface of the titanium-based alloy; preferably, the direct current voltage is 30-60V, and the electrolysis time is 1-3 h; preferably, the electrolyte consists of ammonium fluoride, water and ethylene glycol; wherein the mass fraction of the ammonium fluoride is 0.1-0.3%, and the volume fraction of the water is 1-3%.
Preferably, the step of surface chemical modification treatment is: soaking the titanium-based alloy treated by the step of preparing the porous microstructure in an ethanol solution of a fluorinated polymer, taking out after soaking for a set time, and drying; preferably, the soaking temperature is 50-60 ℃; soaking for 20-30 min; preferably, the fluorinated polymer is perfluorooctyltriethoxysilane or 1,1,2, 2-perfluorodimethylcyclohexane; preferably, the volume fraction of the ethanol solution of the fluorinated polymer is 1 to 3%; preferably, the temperature of the drying treatment is 100-110 ℃, and the time of the drying treatment is 20-30 min.
Preferably, the step of impregnating the lubricant comprises: soaking the titanium-based alloy subjected to surface chemical modification treatment in a lubricant in a low vacuum environment, and taking out to obtain the titanium-based alloy with the bionic super-smooth surface structure; preferably, the low vacuum environment is a vacuum environment with the vacuum degree of 3.0-5.0 Pa; preferably, the soaking treatment time is 20-30 min; preferably, after the soaking treatment is finished, taking out the titanium-based alloy and placing the titanium-based alloy in an inclined manner to remove the redundant lubricant; further preferably, the inclination angle is 10-30 degrees, and the inclined placement time is 1.5-2.5 h.
In still another aspect, the titanium-based alloy with a biomimetic ultra-smooth surface structure prepared by the method of any one of the above or the titanium-based alloy with a biomimetic ultra-smooth surface structure prepared by the method of any one of the above is applied to preparation or application as an anti-biofouling material. Preferably, the anti-biofouling material is mainly a material in the anti-biofouling field of ships, marine engineering, medical instruments, and the like.
Compared with the prior art, the titanium-based alloy with the bionic super-smooth surface structure, the preparation method and the application thereof have at least the following beneficial effects:
in one aspect, an embodiment of the present invention provides a titanium-based alloy with a bionic super-smooth surface structure, where the bionic super-smooth surface structure has a two-stage rough surface structure formed by combining a concave-convex macro structure and a porous micro structure, a lubricant layer covers the two-stage rough surface structure, and the lubricant layer and the two-stage rough surface structure are combined to form the bionic super-smooth surface structure of the titanium-based alloy. Through the design, the concave-convex macroscopic structure can play a good role in protecting the porous microscopic structure, so that the friction resistance of the porous microscopic structure is improved, and the service time of the bionic super-smooth surface is further prolonged; and compared with the titanium-based alloy bionic super-smooth surface with the porous microstructure, the two-stage rough surface structure formed by compounding the concave-convex macroscopic structure and the porous microstructure greatly improves the oil storage capacity and reduces the dissipation rate of the lubricant. Therefore, the titanium-based alloy with the bionic super-smooth surface provided by the embodiment of the invention can effectively inhibit the adhesion of micro or macro organisms, and is applied to the anti-biological fouling fields of ships, ocean engineering, medical instruments and the like.
On the other hand, the preparation method of the titanium-based alloy with the bionic super-smooth surface structure provided by the embodiment of the invention has the advantages of simple and feasible process, low cost and the like, and is suitable for preparing the bionic super-smooth surface structure of large and medium-sized titanium-based alloy samples or parts.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a titanium-based alloy with a biomimetic ultra-smooth surface structure according to an embodiment of the present invention;
fig. 2 is a schematic view of the predetermined array pattern according to the present invention, which is formed by arranging regular polygon patterns, the inscribed circle diameter of the regular polygon being 0.3-1.5mm, wherein, a in fig. 2 is a schematic view of the regular hexagon pattern arrangement, and b in fig. 2 is a schematic view of the regular quadrilateral pattern arrangement;
fig. 3a is a diagram of a laser confocal morphology of a concave-convex macro structure processed on the surface of a titanium-based alloy in example 2 of the present invention, fig. 3 b is a diagram of a laser confocal morphology of a two-stage rough structure composed of a concave-convex macro structure and a porous micro structure processed on the surface of a titanium-based alloy in example 2 of the present invention, and fig. 3 c is a diagram a and a diagram b which reflect the statistical analysis results of the concave depth of the concave-convex macro structure and the two-stage rough structure processed on the surface of a titanium-based alloy in example 2 of the present invention;
fig. 4 is a scanning electron microscope image of a two-stage rough surface structure machined on the surface of a titanium-based alloy according to example 2 of the present invention, in which a in fig. 4 is a scanning electron microscope image showing a concave-convex macro structure, b in fig. 4 is an enlarged view of a square frame in a, c in fig. 4 is an enlarged view of a square frame in b and shows a porous microstructure, and d in fig. 4 is a cross-sectional view of the porous microstructure;
fig. 5 is a scanning electron microscope image of a two-stage rough surface structure machined on the surface of a titanium-based alloy according to example 3 of the present invention, in which a in fig. 5 is a scanning electron microscope image showing a concave-convex macro structure, b in fig. 5 is an enlarged view of a square frame in a, and c in fig. 5 is an enlarged view of a square frame in b and shows a porous micro structure;
fig. 6 is a diagram showing the anti-mussel adhesion of the titanium-based alloy prepared in example 2 of the present invention (wherein, the upper sample piece of a-d in fig. 6 is a control group bare Ti-6Al-4V titanium-based alloy sample piece, the lower sample piece is an experimental group titanium-based alloy bionic super-slippery surface prepared in example 2 of the present invention, e is a mussel foot silk distribution diagram on the surface of the control group after removal of mussels, and f is a mussel foot silk distribution diagram on the surface of the experimental group after removal of mussels);
FIG. 7 shows the super-hydrophobicity of different surfaces (experimental group a: preparation process 1), 3) and 4) of different titanium-based alloys prepared in comparative example 1 according to the present invention, which are characterized by water contact angles after the actual rubbing process; experimental group b: the preparation process is carried out according to the steps 1), 2) and 4) in the embodiment 2 in sequence; example 2 the prepared sample was named control group c);
FIG. 8 shows the super-hydrophobicity of different surfaces (experimental group a: the preparation process is as in 1), 3) and 4) of different titanium-based alloys prepared in comparative example 1 of the present invention, which are characterized by water contact angles, after continuously washing for 25 days; experimental group b: the preparation process is carried out according to the steps 1), 2) and 4) in the embodiment 2 in sequence; example 2 the prepared sample was named control group c).
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The embodiment of the invention provides a titanium-based alloy with a bionic super-smooth surface structure and a preparation method thereof, and the main technical scheme is as follows:
in one aspect, embodiments of the present invention provide a titanium-based alloy with a biomimetic ultra-smooth surface structure, wherein the biomimetic ultra-smooth surface structure has a two-stage rough surface structure (see fig. 4 and 5 for details); the two-stage rough surface structure is formed by compounding a concave-convex macro structure (specifically referring to a diagram a in fig. 4 and a diagram a in fig. 5) and a porous microstructure (specifically referring to a diagram c and a diagram d in fig. 4 and a diagram c in fig. 5). The lubricant layer covers the two-stage rough surface structure of the titanium-based alloy. And the lubricant layer and the two-stage rough surface structure are compounded to form the titanium-based alloy bionic super-smooth surface structure. Wherein, the rough surface structure of the titanium-based alloy surface is grafted with fluorinated polymer, and the lubricant layer covers the two-stage rough surface structure of the titanium-based alloy surface under the action of the fluorinated polymer. Preferably, the fluorinated polymer is perfluorooctyltriethoxysilane or 1,1,2, 2-perfluorodimethylcyclohexane. Preferably, the lubricant is a perfluoropolyether or polydimethylsiloxane.
Here, it should be noted that: "relief macrostructure" refers to a structure having projections and recesses, and the structure of the projections and recesses is visible to the naked eye. And the porous microstructure refers to a porous structure that is not visible to the naked eye, but can be observed by means of a scanning electron microscope.
Preferably, the porous microstructure has a pore size of 20-150nm and a pore depth of 0.2-10 μm.
In the titanium-based alloy with the bionic super-smooth surface structure provided by the embodiment of the invention, the titanium-based alloy surface is prepared into a two-stage rough surface structure formed by compounding the concave-convex macro structure and the porous micro structure, so that on one hand, the concave-convex macro structure can play a role in protecting the porous micro structure, the friction resistance of the porous micro structure is improved, and the service time of the bionic super-smooth surface is prolonged; on the other hand, compared with the titanium-based alloy bionic super-smooth surface with only the porous microstructure, the two-stage rough surface structure formed by compounding the concave-convex macroscopic structure and the porous microstructure greatly improves the oil storage capacity and reduces the dissipation rate of the lubricant.
In order to better prolong the service time of the bionic super-smooth surface, improve the oil storage capacity and reduce the dissipation rate of the lubricant, the embodiment of the invention designs the concave-convex macroscopic structure as follows: comprises a preset array pattern; wherein the predetermined array pattern is formed by arranging a plurality of regular polygon patterns (repeated and densely arranged, the term "densely arranged" herein means that each regular polygon and its adjacent regular polygon have a common edge); wherein, the convex part of the concavo-convex macrostructure corresponds to the line part (i.e. the side of the regular polygon) on each of the patterns (for example, if the pattern is the regular polygon, the side length of the regular polygon is set as the convex part), and the concave part of the concavo-convex macrostructure corresponds to the other part except the line part in each of the patterns (for example, if the pattern is the regular polygon, the area part surrounded by the side length of the regular polygon is set as the concave part); further preferably, the depth of the recess is 30 to 300 μm; the type of the regular polygon pattern is one or more, for example, one or more of regular polygons such as regular triangles, squares, or regular hexagons; preferably, the diameter of the inscribed circle of the regular polygon is 0.3-1.5 mm. Referring to fig. 2, a diagram a in fig. 2 is a schematic diagram of a regular hexagonal pattern arrangement, and a diagram b in fig. 2 is a schematic diagram of a regular quadrilateral pattern arrangement.
On the other hand, the embodiment of the invention provides a preparation method of the titanium-based alloy with the bionic super-smooth surface structure, as shown in fig. 1, the preparation method comprises the following steps:
1) a pretreatment step: cleaning titanium-based alloy with a certain size, and drying for later use;
the titanium-based alloy can be industrial alpha or near alpha type titanium-based alloy (such as Ti-6Al-7Nb, Ti-4Al-1.5Mn, etc.), or alpha + beta type titanium-based alloy (such as Ti-6Al-4V, Ti-3Al-5Mo-4.5V, etc.).
2) Processing a concave-convex macrostructure: the concave-convex macrostructure is prepared on the surface of the titanium-based alloy by physical methods including machining, screen printing etching, laser processing and the like.
The specific shape of the concave-convex macrostructure is as described above, and the detailed description is not repeated here.
3) Preparing a porous microstructure: and (3) taking the titanium-based alloy treated in the step 2) as an anode and a graphite sheet or a platinum sheet as a cathode, inserting the two electrodes into electrolyte at room temperature, and applying direct current voltage to prepare a secondary porous microstructure on the surface of the titanium-based alloy.
The method comprises the following steps: the direct current voltage is 30-60V, the time is 1-3h, and the used electrolyte comprises 0.1-0.3% of ammonium fluoride by mass fraction, 1-3% of water by volume fraction, and the balance of mixed solution of ethylene glycol.
4) Post-treatment: and 3) carrying out surface chemical modification treatment and perfluoropolyether lubricant dipping treatment on the titanium-based alloy treated in the step 3) in sequence to obtain the titanium-based alloy with the bionic super-smooth surface structure.
The surface chemical modification treatment comprises the following steps: soaking the titanium-based alloy treated in the step 3) in an ethanol solution of fluorinated polymer with the volume fraction of 1-3% for 20-30min at the temperature of 50-60 ℃, taking out and drying at the temperature of 100-110 ℃ for 20-30 min;
the dipping treatment steps are as follows: soaking the titanium-based alloy subjected to surface chemical modification treatment in a lubricant, placing the titanium-based alloy in a low-vacuum environment with the vacuum degree of 3.0-5.0Pa for 20-30min, taking out the titanium-based alloy, inclining the titanium-based alloy by 10-30 degrees, placing the titanium-based alloy for 2h, and removing the redundant lubricant to obtain the titanium-based alloy with the bionic super-smooth surface structure.
The titanium-based alloy with the bionic super-smooth surface structure provided and prepared by the embodiment of the invention can effectively inhibit the adhesion of micro or macro organisms, and is suitable for being applied to the anti-biological fouling fields of ships, ocean engineering, medical instruments and the like.
The invention is further illustrated by the following specific experimental examples:
example 1
The embodiment prepares a titanium-based alloy with a bionic super-smooth surface structure, and mainly comprises the following steps:
1) a pretreatment step: cleaning the surface of the Ti-6Al-4V titanium-based alloy, and drying for later use;
2) processing a concave-convex macrostructure: processing a surface concave-convex macro structure comprising a preset array pattern on the surface of the Ti-6Al-4V titanium-based alloy by a machining mode: the method comprises the following specific steps:
engineering drawing: drawing a preset plane densely-arranged regular triangle array pattern, wherein the diameter of an inscribed circle of a regular triangle is 0.5 mm;
performing surface fine engraving on the Ti-6Al-4V titanium-based alloy by using a fine engraving machine, setting the engraving depth to be 300 mu m, and processing a concave-convex macroscopic structure comprising a preset array pattern on the surface of the Ti-6Al-4V titanium-based alloy (wherein a convex part corresponds to the side length of a regular triangle, and a concave part corresponds to the area part enclosed by the side length of the regular triangle);
cleaning the surface of the Ti-6Al-4V titanium-based alloy, and drying at 50 ℃ for later use.
3) Preparing a porous microstructure: and (2) taking the Ti-6Al-4V titanium-based alloy treated in the step 2) as an anode and a platinum sheet as a cathode, inserting the two electrodes into electrolyte at room temperature, applying 50V direct current voltage, and preparing a porous microstructure on the surface of the titanium-based alloy for 2 hours, wherein the electrolyte is a mixed solution of 0.3% of ammonium fluoride by mass fraction, 1% of water by volume fraction and the balance of ethylene glycol.
4) Post-treatment: carrying out surface chemical modification treatment on the Ti-6Al-4V titanium-based alloy treated in the step 3), which comprises the following specific steps: soaking the Ti-6Al-4V titanium-based alloy treated in the step 3) in an ethanol solution of 1,1,2, 2-perfluorodimethylcyclohexane with the volume fraction of 3% for 30min at 50 ℃, taking out and drying for 30min at the temperature of 100 ℃;
and then soaking the Ti-6Al-4V titanium-based alloy subjected to surface chemical modification treatment in a perfluoropolyether lubricant, placing the Ti-6Al-4V titanium-based alloy in a low-vacuum environment with the vacuum degree of 3.0-5.0Pa for 30min, taking out the Ti-6Al-4V titanium-based alloy, inclining the Ti-6Al-4V titanium-based alloy for 30 degrees, placing the Ti-6Al-4V titanium-based alloy for 2h, and removing the redundant perfluoropolyether lubricant to obtain the titanium-based alloy with the bionic super-smooth surface structure.
Example 2
The embodiment prepares a titanium-based alloy with a bionic super-smooth surface structure, and mainly comprises the following steps:
1) a pretreatment step: cleaning the surface of the Ti-6Al-4V titanium-based alloy, and drying for later use;
2) processing a concave-convex macrostructure: preparing a concave-convex macro structure comprising a preset array pattern on the surface of the Ti-6Al-4V titanium-based alloy by a screen printing etching method, and specifically comprising the following steps:
engineering drawing: drawing a preset close-packed regular hexagon array pattern, wherein the diameter of an inscribed circle of a regular hexagon is 1mm, and a schematic diagram is shown as a diagram in fig. 2;
brushing ink and baking plate: uniformly brushing photosensitive ink on the surface of the Ti-6Al-4V titanium-based alloy, and then baking a plate;
exposure and development: exposing the preset pattern area by using a metal halogen lamp, and developing by using a developing solution;
etching: the etching solution is a mixed solution of 10% by mass of nitric acid, 3.5% by mass of hydrofluoric acid and the balance of deionized water, the Ti-6Al-4V titanium-based alloy subjected to exposure and development treatment is subjected to dip-coating and dip-coating treatment at room temperature for 5min, and a concave-convex macro structure comprising a preset array pattern is processed on the surface of the Ti-6Al-4V titanium-based alloy;
and cleaning the Ti-6Al-4V titanium-based alloy by using ethanol and deionized water in sequence, and drying at 50 ℃ for later use.
Fig. 3a is a laser confocal morphology of a concave-convex macrostructure processed on the surface of the titanium-based alloy in example 2, and as can be seen from fig. 3a and c: example 2 the depth of the concave and convex macrostructure recesses machined on the surface of the titanium-based alloy was 35.05 ± 3.77 μm.
3) Preparing a porous microstructure: and (2) taking the Ti-6Al-4V titanium-based alloy treated in the step 2) as an anode and a graphite sheet as a cathode, inserting the two electrodes into electrolyte at room temperature, applying direct current voltage of 60V to prepare a porous microstructure for 1h, wherein the electrolyte is a mixed solution of 0.25% by mass of ammonium fluoride, 1% by volume of water and the balance of ethylene glycol.
At this time, the titanium-based alloy has a rough surface structure formed by compounding a concave-convex macro structure and a porous micro structure, wherein a scanning electron microscope image of the rough surface structure is shown in fig. 4, wherein a in fig. 4 is a scanning electron microscope image showing the concave-convex macro structure, and b in fig. 4 is an enlarged image of a frame in a in fig. a, showing convex portions and concave portions of the concave-convex macro structure; panel c of FIG. 4 is an enlarged view at box in panel b and shows the porous microstructure; fig. 4 d is a cross-sectional view of the porous microstructure, which has a pore depth of 6.67 ± 0.35 μm.
Fig. 3 b shows the laser confocal morphology of the two-stage roughness structure processed on the surface of the titanium-based alloy in example 2, and from the b and c, it can be seen that the depth of the concave part of the two-stage roughness structure formed by compounding the concave-convex macrostructure and the porous microstructure is 27.06 ± 6.87 μm, which is processed on the surface of the titanium-based alloy in example 2.
4) Post-treatment: carrying out surface chemical modification treatment on the Ti-6Al-4V titanium-based alloy treated in the step 3), which comprises the following specific steps: soaking the Ti-6Al-4V titanium-based alloy treated in the step 3) in an ethanol solution of 2 volume percent perfluorooctyltriethoxysilane for 30min at 60 ℃, taking out and drying for 30min at 110 ℃;
and then soaking the Ti-6Al-4V titanium-based alloy subjected to surface treatment in a perfluoropolyether lubricant, placing the Ti-6Al-4V titanium-based alloy in a low-vacuum environment with the vacuum degree of 3.0-5.0Pa for 30min, taking out the Ti-6Al-4V titanium-based alloy, inclining the Ti-6Al-4V titanium-based alloy by 20 degrees, placing the Ti-6Al-4V titanium-based alloy for 2h, and removing the redundant perfluoropolyether lubricant to obtain the titanium-based alloy with the bionic super-smooth surface structure.
Fig. 6 is a diagram showing the anti-mussel adhesion of the titanium-based alloy with the bionic super-slippery surface structure prepared in example 2 (wherein, the upper sample piece of the a-d diagram of fig. 4 is a control group bare Ti-6Al-4V titanium-based alloy sample piece, the lower sample piece is the experimental group titanium-based alloy bionic super-slippery surface prepared in example 2 of the invention, the e diagram is a mussel foot silk distribution diagram of the control group surface after removing mussels, and the f diagram is a mussel foot silk distribution diagram of the experimental group surface after removing mussels).
As can be seen from fig. 6: mussel secretes a large amount of byssus on a control Ti-6Al-4V titanium-based alloy sample piece within 72h, and firmly adheres to the control sample piece; while the titanium-based alloy prepared in example 2 shows that the mussels are close to each other within 72h and secrete byssus to be fixed to each other on the shells of other mussels in a competitive way, and the byssus secretion is rarely carried out on the bionic super-smooth surface of the titanium-based alloy prepared in example 2, thereby showing that: the prepared titanium-based alloy bionic super-smooth surface has good marine organism fouling resistance.
Example 3
The embodiment prepares a titanium-based alloy with a bionic super-smooth surface structure, and mainly comprises the following steps:
1) a pretreatment step: cleaning the surface of the Ti-6Al-4V titanium-based alloy, and drying for later use;
2) processing a concave-convex macrostructure: preparing a concave-convex macro structure comprising a preset array pattern on the surface of the Ti-6Al-4V titanium-based alloy by a laser processing method, and specifically comprising the following steps:
engineering drawing: drawing a preset close-packed regular hexagon array pattern, wherein the diameter of an inscribed circle of a regular hexagon is 0.7mm, and a schematic diagram is shown as a diagram in fig. 2;
performing laser processing on the surface of the Ti-6Al-4V titanium-based alloy by adopting nanosecond laser, setting the processing depth to be 250 mu m, and processing a concave-convex macro structure comprising a preset array pattern on the surface of the Ti-6Al-4V titanium-based alloy; (wherein the convex part corresponds to the side length of the regular hexagon, and the concave part corresponds to the area part surrounded by the side length of the regular hexagon)
Cleaning the surface of the Ti-6Al-4V titanium-based alloy, and drying at 50 ℃ for later use;
3) preparing a porous microstructure: and (2) taking the Ti-6Al-4V titanium-based alloy treated in the step 2) as an anode and a graphite sheet as a cathode, inserting the two electrodes into electrolyte at room temperature, applying a direct current voltage of 30V to prepare a porous microstructure for 1.5h, wherein the electrolyte is a mixed solution of 0.2% of ammonium fluoride by mass fraction, 2% of water by volume fraction and the balance of ethylene glycol.
FIG. 5 is a scanning electron microscope image of example 3 of the present invention after machining a rough surface structure on the surface of a titanium-based alloy, wherein a in FIG. 5 is a scanning electron microscope image showing a concavo-convex macro structure, b in FIG. 5 is an enlarged view of a square frame in a, and c in FIG. 5 is an enlarged view of a square frame in b and shows a porous micro structure;
4) post-treatment: carrying out surface chemical modification on the Ti-6Al-4V titanium-based alloy treated in the step 3): soaking the Ti-6Al-4V titanium-based alloy treated in the step 3) in an ethanol solution of perfluorooctyltriethoxysilane with the volume fraction of 1.5% for 30min at 55 ℃, taking out and drying at 100 ℃ for 30 min;
and then soaking the Ti-6Al-4V titanium-based alloy subjected to surface treatment in a polydimethylsiloxane lubricant, placing the Ti-6Al-4V titanium-based alloy in a low-vacuum environment with the vacuum degree of 3.0-5.0Pa for 30min, taking out the Ti-6Al-4V titanium-based alloy, inclining the Ti-6Al-4V titanium-based alloy at 20 degrees, placing the Ti-6Al-4V titanium-based alloy for 2h, and removing the redundant polydimethylsiloxane lubricant to obtain the titanium-based alloy with the bionic super-smooth surface structure.
Comparative example 1
The two-stage surface roughness structure compounded by the concave-convex macrostructure and the porous microstructure prepared on the surface of the titanium-based alloy has excellent mechanical durability (anti-friction capability) and stability of a lubricant layer for embodying the embodiment of the invention.
Example 2 is now set up as a control experiment. And experimental group a and experimental group b were additionally set. Wherein, experimental group a: the preparation process is carried out according to the steps 1), 3) and 4) in the embodiment 2 in sequence; experimental group b: the preparation process is carried out according to the steps 1), 2) and 4) in the embodiment 2 in sequence; example 2 is control group c.
1. The titanium-based alloy samples prepared in experimental groups a, b and control group c were subjected to a reciprocating abrasion process, and a schematic diagram of the abrasion process is shown in fig. 7, in a specific procedure in which the sample surface was faced with 1200# sandpaper, and a certain weight (50g weight) was applied to the surface, the entire sample was induced to move back and forth on the sandpaper (a single cycle distance of 5cm), and then the change in water contact angle of the sample surface after abrasion was measured.
FIG. 7 shows the superhydrophobicity of different surfaces characterized by water contact angles after an actual abrasion process. It can be clearly seen that after 35 rubbing cycles, the water contact angle of the titanium-based alloy sample prepared in the experimental group a is reduced by 31.7%, the water contact angle of the titanium-based alloy sample prepared in the experimental group b is reduced by 9.6%, and the water contact angle of the titanium-based alloy sample prepared in the control group c is still maintained at about 118 °.
The experimental results show that: the concave-convex macrostructure can improve the friction resistance, and the concave-convex macrostructure is preferentially worn in the actual friction process. The titanium-based alloy sample prepared by the experimental group a is not protected by a concave-convex macroscopic structure, and the porous microscopic structure is directly damaged at the initial stage of wear, so that the water contact angle is greatly reduced. The titanium-based alloy sample prepared in the experimental group b contains a surface concave-convex macro structure, but lacks a porous micro structure, so that the oil storage capacity is reduced in the rubbing process, and the water contact angle is also reduced.
The above results show that: the concave-convex macrostructure and the porous microstructure have a synergistic effect, and the composite dual structure (two-stage rough surface structure) enables the titanium-based alloy surface to have excellent mechanical durability when subjected to mechanical abrasion.
2. To evaluate the long-term effectiveness of the lubricant layer in seawater, samples of titanium-based alloys prepared in the experimental group and the control group were immersed in artificial seawater with constant agitation to accelerate the failure of the lubricant layer. The method comprises the following specific steps: the surfaces of the titanium-based alloy samples prepared in the experimental group and the control group are vertically attached to the inner wall of a beaker filled with artificial seawater, then the artificial seawater solution is stirred by a magnetic stirrer at the speed of 400rpm, the speed equivalent to the seawater is calculated to be about 120m/min, and the stability of the lubricant layer is evaluated by measuring the water contact angle of the bionic super-smooth surface.
Fig. 8 shows that the water contact angles of the titanium-based alloy samples prepared by the experimental groups a and b always keep a descending trend under the continuous flushing for 25 days, while the water contact angle of the titanium-based alloy sample prepared by the control group c always keeps in the interval of 110-116 degrees, and particularly, the water contact angles of the titanium-based alloy samples prepared by the experimental groups a and b suddenly drop by 17% and the water contact angle of the titanium-based alloy sample prepared by the control group c only drops by 5% in the first 10 days of the continuous flushing, which indicates that the lubricant layer of the titanium-based alloy samples prepared by the experimental groups a and b is easy to lose under the continuous flushing condition, so that the water contact angle is reduced and the hydrophobicity is reduced. The specific reason is that the titanium-based alloy prepared by the experimental group a is not protected by the concave-convex macrostructure, and the flow velocity of water in the concave-convex macrostructure in the scouring process can be reduced by the structured surface, so that the loss of the lubricant on the surface layer is reduced. The titanium-based alloy prepared by the experimental group b has a concave-convex macrostructure on the surface, but lacks a porous microstructure, so that the lubricant is quickly lost in the continuous scouring process, and the water contact angle is reduced.
The above results show that: the concave-convex macrostructure and the porous microstructure have a synergistic effect, and a dual structure (two-stage rough surface structure) compounded by the concave-convex macrostructure and the porous microstructure enables the lubricant layer to have long-term effectiveness on the surface of the titanium-based alloy.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A titanium-based alloy having a biomimetic ultra-smooth surface structure, said biomimetic ultra-smooth surface structure comprising:
the two-stage rough surface structure is formed by compounding a concave-convex macroscopic structure and a porous microscopic structure;
a lubricant layer overlying the two-stage rough surface structure;
and the two-stage rough surface structure and the lubricant layer are compounded to form the bionic super-smooth surface structure of the titanium-based alloy.
2. The titanium-based alloy with biomimetic ultra-smooth surface structure according to claim 1,
the two-stage rough surface structure is grafted with fluorinated polymer, so that the lubricant layer is covered on the two-stage rough surface structure under the action of the fluorinated polymer;
preferably, the fluorinated polymer is perfluorooctyltriethoxysilane or 1,1,2, 2-perfluorodimethylcyclohexane;
preferably, the lubricant in the lubricant layer is perfluoropolyether or polydimethylsiloxane;
preferably, the lubricant in the lubricant layer is in a viscous state, and further preferably, the viscosity of the lubricant is in a range of 5 to 250cSt at 40 ℃.
3. The titanium-based alloy with biomimetic ultra-smooth surface structure according to claim 1 or 2,
the concave-convex macro structure comprises a preset array pattern; the preset array pattern is formed by arranging a plurality of regular polygon patterns; wherein the convex parts of the concave-convex macrostructure correspond to the line parts on the regular polygon pattern, and the concave parts of the concave-convex macrostructure correspond to the other parts except the line parts in each pattern;
preferably, the depth of the concave part is 30-300 μm;
preferably, the diameter of the inscribed circle of the regular polygon is 0.3-1.5 mm;
preferably, the preset array pattern comprises one or more shapes of regular polygon patterns;
preferably, in the predetermined array pattern, each regular polygon has a common edge with its adjacent regular polygon.
4. The titanium-based alloy with a biomimetic ultra-smooth surface structure according to claim 1, wherein the porous microstructure has a pore size of 20-150nm and a pore depth of 0.2-10 μm.
5. The method for preparing a titanium-based alloy having a biomimetic ultra-smooth surface structure according to any of claims 1-4, comprising the steps of:
processing a concave-convex macrostructure: processing a concave-convex macro structure on the surface of the titanium-based alloy;
preparing a porous microstructure: carrying out anodic oxidation treatment on the titanium-based alloy treated by the step of processing the concave-convex macrostructure, and preparing a porous microstructure on the surface of the titanium-based alloy;
post-treatment: and sequentially carrying out surface chemical modification treatment and lubricant impregnation treatment on the titanium-based alloy treated by the step of preparing the porous microstructure to obtain the titanium-based alloy with the bionic super-smooth surface structure.
6. The method for preparing titanium-based alloy with bionic super-smooth surface structure according to claim 5,
in the step of processing the concave-convex macrostructure: processing a concave-convex macro structure on the surface of the titanium-based alloy by a physical method; preferably, the physical method comprises one or more of machining, screen printing etching and laser processing; and/or
Before the step of processing the concave-convex macroscopic structure, the method also comprises a pretreatment step; wherein the pretreatment step comprises: and cleaning and drying the titanium-based alloy.
7. The method for preparing a titanium-based alloy having a biomimetic ultra-smooth surface structure according to claim 5, wherein in the step of preparing the porous microstructure:
taking the titanium-based alloy treated by the step of processing the concave-convex macroscopic structure as an anode, and taking a graphite sheet or a platinum sheet as a cathode; inserting an anode and a cathode into the electrolyte, applying direct current voltage to carry out electrolysis, and preparing a porous microstructure on the surface of the titanium-based alloy;
preferably, the direct current voltage is 30-60V, and the electrolysis time is 1-3 h;
preferably, the electrolyte consists of ammonium fluoride, water and ethylene glycol; wherein the mass fraction of the ammonium fluoride is 0.1-0.3%, and the volume fraction of the water is 1-3%.
8. The method for preparing the titanium-based alloy with the bionic super-smooth surface structure according to claim 5, wherein the step of surface chemical modification treatment comprises the following steps:
soaking the titanium-based alloy treated by the step of preparing the porous microstructure in an ethanol solution of a fluorinated polymer, taking out after soaking for a set time, and drying;
preferably, the soaking temperature is 50-60 ℃; soaking for 20-30 min;
preferably, the fluorinated polymer is perfluorooctyltriethoxysilane or 1,1,2, 2-perfluorodimethylcyclohexane;
preferably, the volume fraction of the ethanol solution of the fluorinated polymer is 1 to 3%;
preferably, the temperature of the drying treatment is 100-110 ℃, and the time of the drying treatment is 20-30 min.
9. The method for preparing a titanium-based alloy having a biomimetic ultra-smooth surface structure according to claim 5 or 8, wherein the step of impregnating with a lubricant comprises:
soaking the titanium-based alloy subjected to surface chemical modification treatment in a lubricant in a low vacuum environment, and taking out to obtain the titanium-based alloy with the bionic super-smooth surface structure;
preferably, the low vacuum environment is a vacuum environment with the vacuum degree of 3.0-5.0 Pa;
preferably, the soaking treatment time is 20-30 min;
preferably, after the soaking treatment is finished, taking out the titanium-based alloy and placing the titanium-based alloy in an inclined manner to remove the redundant lubricant; further preferably, the inclination angle is 10-30 degrees, and the inclined placement time is 1.5-2.5 h.
10. Use of a titanium-based alloy with a biomimetic ultra-smooth surface structure according to any of claims 1-4 or a titanium-based alloy with a biomimetic ultra-smooth surface structure prepared by a method according to any of claims 5-9 in the preparation or as an anti-biofouling material.
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| CN102021628A (en) * | 2009-09-11 | 2011-04-20 | 中国科学院兰州化学物理研究所 | Method for preparing metal titanium or titanium alloy super-oleophobic surface |
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| CN103668390A (en) * | 2014-01-02 | 2014-03-26 | 四川大学 | Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof |
| CN110952124A (en) * | 2018-09-27 | 2020-04-03 | 中国科学院宁波材料技术与工程研究所 | Antifouling titanium alloy material based on bionic super-smooth surface, and preparation method and application thereof |
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| CN102021628A (en) * | 2009-09-11 | 2011-04-20 | 中国科学院兰州化学物理研究所 | Method for preparing metal titanium or titanium alloy super-oleophobic surface |
| CN102191529A (en) * | 2011-04-29 | 2011-09-21 | 中国科学院合肥物质科学研究院 | Honeycomb ordered titanium dioxide nanotube array film and preparation method thereof |
| CN103668390A (en) * | 2014-01-02 | 2014-03-26 | 四川大学 | Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof |
| CN110952124A (en) * | 2018-09-27 | 2020-04-03 | 中国科学院宁波材料技术与工程研究所 | Antifouling titanium alloy material based on bionic super-smooth surface, and preparation method and application thereof |
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