CN114133612B - Bionic super-spreading surface and preparation method thereof - Google Patents
Bionic super-spreading surface and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bionic super-spreading surface and a preparation method thereof, belonging to the technical field of super-hydrophilic materials, wherein the surface is provided with a micron convex structure, the convex structure is tightly arranged on the surface in a honeycomb structure mode, the bottom surface of the convex structure is a polygon with the number of sides not less than 6, and the bottom surface of the convex structure is finally round along with the increase of the number of sides; the diameter of the cross section of the structure of the bulge structure is gradually reduced from the bottom to the top, namely the distance between two adjacent bulges is gradually increased from the bottom to the top. The invention is inspired by the microstructure of the natural Philippine grass blades, optimizes the complex natural plant surface into a simple structure and carries out the preparation of the artificial surface; the obtained surface has more excellent super-spreading performance, and has super-fast spreading speed and super-large spreading area. The bionic super-spreading surface can quickly evaporate liquid on the surface, has a very obvious cooling effect on the surface, and can be used in a cooling system of electronic equipment.
Description
Technical Field
The invention belongs to the technical field of super-hydrophilic materials, and particularly relates to a bionic super-spreading surface and a preparation method thereof.
Background
The super-hydrophilic surface is a special wetting surface, is commonly existed in the nature, daily life and industrial process, and is essential, such as directional transportation of water/inorganic salt in plant channel, spraying of pesticide on leaf blade, exploitation of underground crude oil, etc. In the research process of the super-hydrophilic surface, people introduce a more complex structure on the surface, further improve the spreading rate of liquid on the surface and further increase the spreading area, so that the super-spreading surface is prepared, and the super-spreading surface can be widely applied to the aspects of ink-jet printing, biomedical analysis, electronic device cooling, seawater desalination, petroleum recovery and the like. Introducing a nano porous structure: the titanium dioxide sol is used for modifying nano titanium dioxide particles on the silicon chip and the glass sheet substrate to ensure that the surface has super spreading performance, a small amount of water is dripped, a layer of uniform water film can be arranged on the surface, the surface has conductivity, and the method can be applied to pattern printing (Advanced Functional Materials, 2016, 26, 9017-9017.). Introducing a micro-nano composite structure: field newspaperA superspreading surface simulating the cornea of an animal eye is provided, and a composite structure of micro-channels and nano-wires is arranged on the surface, so that 2 microliter of water can be spread to 23.72mm 2 The spreading speed can also reach higher speed, and the method is used in the fields of invisible eyes, medical endoscopes, unmanned aerial vehicle lenses and the like which need to keep clear vision (Advanced Materials, 2021, 2007152). Jiang Lei et al prepared a microstructured nanochannel with long lasting super-spreading properties by a simple one-step anodization process and utilized this property to allow the droplets to completely spread on the surface in a short time for efficient heat dissipation (iScience, 2021, 24, 102334.).
With the change of science and technology, the data generation amount and the communication speed of electronic products are greatly improved, people's demands for electronic products tend to be more efficient and smaller in size, which results in higher heat flow, in this case, if the heat dissipation effect of the electronic products is not good, the relative failure rate is increased, the reliability is reduced and the service life is shortened, so that the efficiency of a heat dissipation system needs to be improved. At present, common device heat dissipation methods include air cooling heat dissipation, radiation heat dissipation, liquid cooling heat dissipation and the like, wherein liquid evaporation heat dissipation attracts attention due to high cooling speed, large heat dissipation area and more ideal heat dissipation effect. In the heat dissipation process, the larger the spreading area of the liquid on the surface is, the thinner the thickness of the formed liquid film is, and the larger the effective cooling area is; the faster the spreading speed, the faster the updating speed of the cooling surface, and the more remarkable the cooling effect. Therefore, the super-hydrophilic surface has a very wide application prospect in the aspect of evaporation and heat dissipation.
However, the spreading speed and the spreading area of the surface liquid drop of the disclosed structure cannot reach a higher level at the same time, so that the evaporation speed of the liquid is limited, the effect of cooling the surface is not significant, and the requirement of people on cooling the electronic equipment cannot be met. Based on the situation, the invention provides a bionic super-spreading surface and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defect that the liquid drops on the super-spreading surface cannot simultaneously have quick spreading and large-area spreading performance, improve the evaporation speed of the liquid drops on the surface and further have obvious cooling effect; based on the research on the spreading behavior of liquid drops on tropical herbaceous plant Philippine grass leaves, the microstructure of the surface of the leaves of a natural plant is simulated, a micro-convex structure which is tightly arranged in a honeycomb structure is extracted, and the micro-liquid drops can be rapidly spread to an overlarge area on the whole surface in a non-directional manner.
The invention is inspired by a tropical terrestrial plant ruelian grass originally produced in Brazil, and liquid drops can be quickly spread on the leaves of the tropical terrestrial plant ruelian grass to form an ultrathin liquid film, so that the liquid film is quickly evaporated, and the leaves are cooled. According to the invention, by observing the microstructure of the Lueli grass blade, 5 different structures are found, wherein the most representative and largest structure is a protruding structure closely arranged in a honeycomb-like structure, and the structure is extracted and optimized to obtain a surface formed by closely arranging single micro protruding structures in the honeycomb structure.
The bionic super-spreading surface is provided with a micron convex structure which is regularly arranged on the surface in a honeycomb structure mode, the bottom surface of the convex structure is a polygon with the number of sides not less than 6, and the bottom surface of the convex structure is finally round with the increase of the number of sides, and is preferably a convex with the bottom part being a regular hexagon.
The diameter of the cross section of the convex structure is gradually reduced from the bottom to the top, namely the distance between two adjacent protrusions is gradually increased from the bottom to the top.
The diameter range of the circumcircle of the bottom shape of the bulge structure is 1 to 500 mu m, and the preferable range is 100 to 200 mu m.
The distance between the bottom edges of the micro-bump structures is not more than 1/4 of the diameter of the circumcircle of the bottom structure, and is preferably less than 1/10.
The ratio of the diameter of the circumcircle of the bottom shape of the convex structure to the height of the convex structure is 1/3~3, and preferably 1/2~2.
Intrinsic contact angle of the surface material is less than or equal to 60 °: hydrophilic materials such as polyvinyl alcohol, polyamide, metallic aluminum and the like, and the contact angle is less than 60 degrees; or polyurethane, polydimethylsiloxane, polystyrene, or the like, which can be modified by hydrophilicity to reduce the intrinsic contact angle of the material to 60 ° or less, preferably 10 ° or less.
The micro-convex structure is provided with different secondary structures, such as a micro-step structure, a nano-ball structure or a micro-step structure and a nano-ball structure.
The surface preparation process comprises the following steps:
(1) Preparing a base model of the bionic surface by adopting 3d printing, and performing complex shape on the model to obtain a reverse template; or directly preparing a reverse template by adopting a breathing pattern method or a photoetching method;
the model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing the polydimethylsiloxane prepolymer and a curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer to obtain a mixed glue solution, wherein: the weight ratio of the polydimethylsiloxane prepolymer glue solution to the curing agent glue solution is 10: 1; defoaming the mixed glue solution by using an ultrasonic and vacuumizing method, pouring the mixed glue solution above a template, defoaming by using a vacuumizing method, and curing at the temperature of 60-80 ℃ to obtain a polydimethylsiloxane reverse template;
the specific process for preparing the reverse template by the breathing pattern method comprises the following steps: 25mg/mL of polystyrene in chloroform, and volatilizing the solvent at 75% RH to obtain a polystyrene countertemplate;
preparing a reverse template by a photoetching method: photoetching a silicon wafer to form a reverse template;
(2) The surface material is different from the reverse template, and the reverse template is directly subjected to complex forming to obtain a surface structure; if the materials of the surface material and the reverse template are the same, after the reverse template is subjected to hydrophobic modification, the modified reverse template is subjected to reshaping by using the surface material to obtain a surface structure with the same structure as the basic model;
(3) If the intrinsic contact angle of the surface structure obtained in the step (2) is less than or equal to 60 degrees, the surface structure is a final surface structure;
and (3) if the intrinsic contact angle of the surface structure obtained in the step (2) is larger than 60 degrees, carrying out hydrophilic modification to obtain the final surface structure.
The step (2) of performing hydrophobic modification on the reverse template comprises the following steps: in a plasma instrument, oxygen is used for discharging the surface, and the power is 50-150w; the time is 1-4min; and then modifying the surface with a fluorosilane vapor at 80-120 deg.C, wherein the fluorosilane is selected from one of heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltriethoxysilane and dodecafluoroheptylpropyltrimethoxysilane.
Intrinsic contact angle of the surface material is less than or equal to 60 °: hydrophilic materials such as polyvinyl alcohol, polyamide, metallic aluminum and the like, and the contact angle is less than 60 degrees; or polyurethane, polydimethylsiloxane, polystyrene, or the like, which can be modified by hydrophilicity to reduce the intrinsic contact angle of the material to 60 ° or less, preferably 10 ° or less.
The specific process of adopting polyvinyl alcohol for reshaping is as follows: mixing polyvinyl alcohol powder with molecular weight of 89000-98000 with water and dimethyl sulfoxide according to a mass ratio of 20:45, heating and stirring in a water bath until the solution is dissolved, pouring the solution onto a polydimethylsiloxane reverse template, and putting the polydimethylsiloxane reverse template into a refrigerator for curing and demolding.
The specific procedure for the reshaping with polyamide is as follows: heating the polyamide to molten state, pouring the polyamide onto a polydimethylsiloxane reverse template, cooling and solidifying to obtain the surface with the same structure as the basic model
The concrete process of adopting polyurethane to carry out the reshaping is as follows: adding polyurethane into solvent N, N-dimethylformamide, heating and stirring to completely dissolve the polyurethane, then cooling the solution to room temperature, pouring the solution onto a polydimethylsiloxane reverse template in a fume hood until the solvent is completely volatilized, and obtaining the structural surface of the polyurethane.
The specific process of adopting polystyrene to carry out the reshaping is as follows: adding polystyrene into toluene, mechanically stirring at room temperature until the polystyrene is completely dissolved, and then pouring the solution onto a polydimethylsiloxane reverse template in a fume hood until the toluene is completely volatilized to obtain the structural surface of the polystyrene.
The step (3) of hydrophilic modification refers to the step of processing the surface structure in the step (2) by adopting an oxygen plasma instrument, or modifying stable hydrophilic groups on the surface structure in the step (2) or spraying a hydrophilic layer on the surface structure in the step (2).
The stable hydrophilic group is modified on the surface structure of the step (2) by grafting an aminosilane coupling agent on the surface structure of the step (2); spraying the hydrophilic coating on the surface structure in the step (2) means spraying hydrophilic titanium dioxide sol on the surface structure in the step (2).
The specific process of grafting the amino silane coupling agent is as follows: 50 μ L of 3-aminopropyltriethoxysilane was placed in a vacuum desiccator with the surface of the structure after 1min of 100W plasma treatment at 10% -3 Vacuumizing for 30min under the vacuum condition of Pa, sealing, and heating in an oven at 120 ℃ for 2h to finish hydrophilic modification.
The preparation process of the titanium dioxide sol comprises the following steps: mixing polyvinyl alcohol with the molecular weight of 34000 with deionized water, heating and stirring at 80 ℃, standing and defoaming to obtain a 30wt% polyvinyl alcohol aqueous solution; then 0.65 g titanium dioxide nanoparticles P25 was mixed with 4 mL deionized water, 5 mL ethanol, 1.2g 30wt% aqueous polyvinyl alcohol solution and stirred overnight at room temperature to dissolve and obtain a uniform titanium dioxide sol.
The ultrasonic time for removing bubbles of the mixed solution is 5-15min, and the vacuum degree of the vacuum pumping is 10 -2 -10 -4 Pa, vacuum defoaming time is 10-25min.
The bionic super-spreading surface has more excellent performance than a natural Philippine grass blade, and can enable liquid drops to be quickly spread to an ultra-large area in all directions on the whole surface to obtain a very thin liquid film. The function comes from the microstructure of the surface, the micron-sized hemispherical structure with hexagons closely arranged, and the structure provides Laplace pressure gradient and capillary force for the movement of liquid, so that micro liquid drops can rapidly move and spread under the condition of neglecting gravity. When the liquid drop is initially contacted with the surface, the Laplace pressure gradient drives the liquid drop to rapidly move towards the bottom end and enter the structure gap due to the reduction of the gap between the adjacent hemispheres from the top end of the structure to the bottom end of the structure; in the structural gap, the liquid is driven by the capillary force of the multiple layers to rapidly and horizontally flow; because the lowest end has the smallest capillary radius and the largest capillary pressure on the liquid, the liquid flowing speed at the bottom is the fastest, and the liquid at the upper layer moves towards the bottom layer, is supplemented into the gap at the lowest layer and finally reaches the largest spreading area. The bionic surface has the property of super spreading through the synergistic effect of capillary force and Laplace pressure, so that the evaporation of liquid on the surface is accelerated, and a more remarkable cooling effect is obtained.
1) The main structure described in the invention is a micro structure, and compared with a nano structure surface, the preparation method is simpler and the structure is easier to control.
2) The invention has lower requirement on the substrate material, and can select various materials to prepare the final surface according to the requirement after the preparation of the template is completed, thereby having wider selection.
3) The surface prepared by the method has the advantages of ultra-fast spreading speed and ultra-large spreading area, so that the liquid can be rapidly spread on the surface to form a very thin liquid film, and the practical application of the surface is facilitated.
Compared with the prior art, the invention has the advantages that: the liquid drop has two performances of ultra-fast spreading speed and ultra-large spreading area on the whole surface, and the preparation method is simple and can be widely applied to various materials.
Drawings
FIG. 1 is an optical view of a natural Philippine leaf according to the invention;
FIG. 2 is a microstructure view of the surface of a natural Philippine leaf of the present invention;
FIG. 3 is a top view of the structure of the biomimetic hyper-spreading surface provided in embodiment 1 of the present invention;
FIG. 4 is a side view of the structure of a biomimetic hyper-spreading surface provided in example 1 of the present invention;
FIG. 5 is a schematic diagram showing the variation of the liquid spreading area between example 1 and the natural Lilium Candidum surface, wherein the same amount of deionized water is 1 μ L;
FIG. 6 is a top view and a side view of the structure of the biomimetic hyper-spreading surface provided in embodiment 5 of the present invention: (a) a top view, (b) a side view;
FIG. 7 is a top view and a side view of the structure of the biomimetic hyper-spreading surface provided in embodiment 6 of the present invention: (a) a top view, (b) a side view;
fig. 8 is a structure of the biomimetic hyper-spreading surface provided in embodiment 10 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods. The PDMS prepolymer used in the examples and the curing agent used therewith were selected from Dow Corning Corporation, USA, model SYLGARD (R) 184.
Example 1:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing renaturation on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And performing hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, as shown in fig. 3 and 4, the prepared convex structure on the surface has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 150 mu m, the height of the convex is 150 mu m, and the space between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
As shown in FIG. 5, 1 μ L of DI water was rapidly spread as a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 4.7cm within 2.6s 2 While the maximum spreading area within the natural Philippine grass blades 9s was reached, which was about 2.1cm 2 。
Example 2:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, and pouring the mixed glue solutionInto the upper part of the formwork and passes through it again 10 -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing complex shape on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a polygon with 7 sides and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of a circumcircle of the heptagon is 150 mu m, the height of the convex is 150 mu m, and the average distance of the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 2.4cm within 10 seconds 2 。
Example 3:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: the polydimethylsiloxane prepolymer and a curing agent matched with the polydimethylsiloxane prepolymer are mixed into a two-component glue solutionUniformly mixing according to the mass ratio of 10 to 1 to obtain a mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing renaturation on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a polygon with 8 sides and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumcircle of the octagon is 150 mu m, the height of the convex is 150 mu m, and the average distance of the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 3.1cm within 8 seconds 2 。
Example 4:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing renaturation on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a polygon with twelve sides, and the top is gradually changed into a circular bulge. The sizes of the prepared convex structures are that the diameter of a circumscribed circle of the dodecagon is 150 mu m, the height of the convex is 150 mu m, and the average distance of the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 3.8cm within 5s 2 。
Example 5:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a reverse template of the bionic surface by adopting a breathing pattern method: 25mg/mL of polystyrene in chloroform, and volatilizing the solvent at 75% RH to obtain a polystyrene template;
(2) Uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and performing 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min to obtain mixed glue solution -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, curing for 2h at 65 ℃, reshaping the reverse template obtained in the step (1), and dissolving the polystyrene reverse template by using chloroform after curing to obtain the structural surface of polydimethylsiloxane;
(3) And performing hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, as shown in fig. 6, the prepared surface has a convex structure with a shape as follows: a semi-ellipsoidal projection. The sizes of the prepared convex structures are that the radius of the hemispherical convex is about 4 mu m, the height of the convex is 16 mu m, the convex structures are closely arranged, and the average distance is 0 mu m. The prepared micron convex structure has smooth surface and no secondary structure.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 6cm within 10s 2 。
Example 6:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Directly preparing a reverse template with a bionic surface by adopting a photoetching method (a 100-crystal-form monocrystalline silicon wafer);
(2) Uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and performing 60W ultrasonic treatment on the mixed glue solution for 10 min and 10W ultrasonic treatment on the mixed glue solution -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under a Pa vacuum degree, curing for 2h at 65 ℃, performing reshaping on the counter template obtained in the step (1), placing the counter template into an ethanol solution after curing, and performing ultrasonic treatment to accelerate demolding to obtain the structural surface of polydimethylsiloxane;
(3) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, as shown in fig. 7, the prepared protruding structure on the surface has the following appearance: and (4) hemispherical bulges. The sizes of the prepared convex structures are that the diameter of the bottom circle of the hemispherical convex is about 8 μm, the height is about 9 μm, and the average interval of the convex structures is 2 μm. The prepared micron convex structure has smooth surface and no secondary structure.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 3.2cm within 10 seconds 2 。
Example 7:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Directly preparing a reverse template with a bionic surface by adopting a photoetching method (a 100-crystal-form monocrystalline silicon wafer);
(2) The polydimethylsiloxane prepolymer and the curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer are mixed according to the mass ratio of 10Mixing to obtain mixed glue solution, and treating with 60W ultrasonic for 10 min to 10 -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under a Pa vacuum degree, curing for 2h at 65 ℃, performing reshaping on the counter template obtained in the step (1), placing the counter template into an ethanol solution after curing, and performing ultrasonic treatment to accelerate demolding to obtain the structural surface of polydimethylsiloxane;
(3) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared protruding structure on the surface has the following appearance: and (4) hemispherical bulges. The sizes of the prepared convex structures are that the diameter of the bottom circle of the hemispherical convex is about 1 μm, the height is about 3 μm, and the average interval of the convex structures is 0.1 μm. The prepared micron convex structure has smooth surface and no secondary structure.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 3.8cm within 12 seconds 2 。
Example 8:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, and pouring the mixed glue solution onto a templateThen, again through 10 -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing complex shape on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a circular bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 500 mu m, the height of the convex is 500 mu m, and the distance between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 4.5cm within 3.2s 2 。
Example 9:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is subjected to replica molding to obtain a reverse template, and the specific preparation method comprises the following steps: the polydimethylsiloxane prepolymer and the curing agent matched with the polydimethylsiloxane prepolymer are mixed into a two-component glue solution according to the mass ratioUniformly mixing according to the proportion of 10 -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing complex shape on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 450 mu m, the height of the convex is 150 mu m, and the distance between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is hydrophilically treated with an oxygen plasma instrument, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structured surface has super-spreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to a uniform liquid film, reaching a maximum spreading area of about 4.1cm within 9s 2 。
Example 10:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step 2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing renaturation on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(3) The surface of the resulting structure is hydrophilically modified by uniformly spraying a layer of hydrophilic titanium dioxide sol onto the surface in an amount of about 0.5g/cm 2 And standing at room temperature until the surface is dried to obtain a hydrophilic surface.
The preparation process of the titanium dioxide sol comprises the following steps: mixing polyvinyl alcohol with the molecular weight of 34000 with deionized water, heating and stirring at 80 ℃, standing and defoaming to obtain a 30wt% polyvinyl alcohol aqueous solution; then 0.65 g titanium dioxide nano particles P25 are mixed with 4 mL deionized water, 5 mL absolute ethyl alcohol and 1.2g of 30wt% polyvinyl alcohol aqueous solution, and stirred overnight at room temperature to dissolve the titanium dioxide nano particles, so that uniform titanium dioxide sol is obtained.
In this embodiment, as shown in fig. 8, the prepared surface has a convex structure with a shape as follows: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a circular bulge. The sizes of the prepared microstructures were that the diameter of the circumscribed circle of the regular hexagon was 150 μm, the height of the protrusions was 150 μm, and the pitch of the protrusion structures was 20 μm. The prepared micro-convex structure also has a secondary step-shaped structure, the average layer height is 10 mu m, and nano titanium dioxide small spherical particles are uniformly distributed on the surface.
In this example, after the surface is sprayed with the hydrophilic titanium dioxide sol, the intrinsic contact angle of the surface is reduced to about 0 °, and the resulting structure surface has super-spreading properties.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 4.3cm within 2.8s 2 。
Example 11:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a reverse template of the bionic surface by adopting a breathing pattern method: 25mg/mL of polystyrene in chloroform, and volatilizing the solvent at 75% RH to obtain a polystyrene template;
(2) Uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and performing 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min to obtain mixed glue solution -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, curing for 2h at 65 ℃, reshaping the reverse template obtained in the step (1), and dissolving the polystyrene reverse template by using chloroform after curing to obtain the structural surface of polydimethylsiloxane;
(3) The surface of the resulting structure is hydrophilically modified by spraying a layer of hydrophilic titanium dioxide sol uniformly onto the surface in an amount of about 0.5g/cm 2 And standing at room temperature until the surface is dried to obtain a hydrophilic surface.
In this embodiment, the prepared surface protrusion structure has the following appearance: a semi-ellipsoidal projection. The sizes of the prepared convex structures are that the radius of the semi-ellipsoidal convex is about 4 mu m, the convex structures are closely arranged, and the average distance is 0 mu m. The surface of the prepared micro-convex structure has a nano-bead structure.
In this example, after spraying the hydrophilic titanium dioxide sol onto the surface, the intrinsic contact angle of the surface was reduced to about 0 °, and the resulting structure surface had superspreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 6cm within 10s 2 。
Example 12:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Compounding a polydimethylsiloxane reverse template by using polyvinyl alcohol with the molecular weight of 89000-98000 to obtain a surface with the same structure as the basic model, wherein the obtained structure surface is a hydrophilic surface without hydrophilic treatment; the polyvinyl alcohol reshaping process is that polyvinyl alcohol powder with molecular weight of 89000-98000, water and dimethyl sulfoxide are mixed according to the mass ratio of 20:45, stirring and heating in a water bath at 90 ℃ for 3 hours until the mixture is dissolved, pouring the solution onto a polydimethylsiloxane reverse template, putting the polydimethylsiloxane reverse template into a refrigerator at-20 ℃ for 6 hours, and then curing and demolding.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 150 mu m, the height of the convex is 150 mu m, and the space between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, the final superspread surface material is polyvinyl alcohol gel, the intrinsic contact angle of the material is 4 °, and the final structure surface has superspread performance.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 2.3cm within 2.8s 2 。
Example 13:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia grass by adopting a 3d printing method;
(2) The model is subjected to replica molding to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) The method is characterized in that a polyamide material (JCC-PA 6106 polyamide) is used for carrying out the renaturation of a polydimethylsiloxane reverse template, and the specific process is as follows: heating JCC-PA6106 polyamide to 120 ℃ to be molten, pouring the molten polyamide on a polydimethylsiloxane reverse template, cooling and solidifying at room temperature to obtain the surface with the same structure with a basic model, wherein the obtained structural surface is a hydrophilic surface without hydrophilic treatment.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 150 mu m, the height of the convex is 150 mu m, and the space between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, the final ultra-spreading surface material is polyamide plastic with a molecular weight of 340, and this material is a hydrophilic material, and the final structural surface has ultra-spreading properties.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 2.6cm within 10 seconds 2 。
Example 14:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) And (3) carrying out reshaping on the polydimethylsiloxane reverse template obtained in the step (2) by using thermoplastic polyurethane (Elastollan 1195A) to obtain a surface with the same structure as the basic model, wherein the specific process comprises the following steps: adding polyurethane into a solvent N, N-dimethylformamide to enable the concentration of the polyurethane in the solvent to be 10wt%, mechanically stirring at 70 ℃ to enable the polyurethane to be completely dissolved, then cooling the solution to room temperature, pouring the solution onto a polydimethylsiloxane reverse template in a fume hood until the solvent is completely volatilized to obtain the structural surface of the polyurethane;
(4) And (3) carrying out hydrophilic modification on the surface of the obtained structure by grafting an aminosilane coupling agent on the surface by a gas-phase grafting method: 50 mu.L of 3-aminopropyltriethoxysilane and 100W of plasma were treated for 1minThe urethane structured surface is placed in a vacuum dryer at 10 -3 Vacuumizing for 30min under the vacuum condition of Pa, sealing, and heating in an oven at 120 ℃ for 2h to finish hydrophilic modification.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a circular bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 150 mu m, the height of the convex is 150 mu m, and the space between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface was grafted with the hydrophilic silane coupling agent, the intrinsic contact angle of the polyurethane surface was reduced to about 10 °, and the resulting structure surface had super-spreading properties.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 4.3cm within 2.8s 2 。
Example 15:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a base model of the bionic surface by adopting a 3d printing method;
(2) The model is subjected to replica molding to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Compounding the polydimethylsiloxane countertemplate obtained in the step 2) by using polystyrene with the average molecular weight of 260000 to obtain a surface with the same structure as the basic model, wherein the specific process comprises the following steps: adding polystyrene with the average molecular weight of 260000 into toluene to enable the concentration of the polystyrene in the toluene to be 50wt%, mechanically stirring the solution at room temperature until the polystyrene is completely dissolved, and pouring the solution into a polydimethylsiloxane reverse template in a fume hood until the toluene is completely volatilized to obtain the structural surface of the polystyrene;
(4) The surface of the resulting structure is hydrophilically modified by uniformly spraying a layer of hydrophilic titanium dioxide sol onto the surface in an amount of about 0.5g/cm 2 And standing at room temperature until the surface is dried to obtain a hydrophilic surface.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge.
In this example, the sizes of the prepared bump structures are that the diameter of the circumscribed circle of the regular hexagon is 150 μm, the height of the bump is 150 μm, and the pitch of the bump structures is 10 μm. The prepared micro-convex structure also has a secondary step-shaped structure, the average layer height is 10 mu m, and nano titanium dioxide small spherical particles are uniformly distributed on the surface.
In this example, after the surface was sprayed with the hydrophilic titanium dioxide sol, the intrinsic contact angle of the polystyrene surface was reduced to about 0 °, and the resulting structure surface had a property of super spreading.
1 μ L of deionized water was rapidly spread to form a uniform liquid film on the surface of the structure obtained in this example, reaching a maximum spreading area of about 4.3cm within 2.8s 2 。
Example 16:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Pumping under Pa vacuum degreeRemoving bubbles from the mixed glue solution by vacuum for 10 min, pouring the mixed glue solution above the template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing renaturation on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And carrying out hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 150 mu m, the height of the convex is 150 mu m, and the space between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this embodiment, after the surface is subjected to hydrophilic treatment by an oxygen plasma instrument, the surface is placed in air at room temperature for 30min (the hydrophilic property of the surface after the hydrophilic treatment is actually unstable, and as the placing time increases, the intrinsic contact angle of the material is different, and the longer the time, the larger the intrinsic contact angle), the intrinsic contact angle of the surface is raised to about 30 °, and the finally obtained structure surface still has the property of superspreading.
1 μ L of deionized water was rapidly spread on the surface of the structure obtained in this example to form a uniform liquid film, reaching a maximum spreading area of about 2.4cm within 5 seconds 2 。
Example 17:
the preparation method of the bionic super-spreading surface comprises the following steps:
(1) Preparing a basic model imitating the surface of the natural ruelia grass by adopting a 3d printing method;
(2) The model is modeled to obtain a reverse template, and the specific preparation method comprises the following steps: uniformly mixing polydimethylsiloxane prepolymer and curing agent double-component glue solution matched with the polydimethylsiloxane prepolymer in a mass ratio of 10 to 1 to obtain mixed glue solution, and carrying out 60W ultrasonic treatment for 10 min and 10W ultrasonic treatment for 10 min -3 Removing bubbles from the mixed glue solution by vacuumizing for 10 min under the condition of Pa vacuum degree, pouring the mixed glue solution above a template, and passing through the template again for 10 min -4 Removing bubbles by a method of vacuumizing for 25min under the Pa vacuum degree, and then curing for 2h at 65 ℃ to obtain a polydimethylsiloxane reverse template;
(3) Placing the polydimethylsiloxane reverse template obtained in the step (2) in a plasma treatment instrument, performing discharge treatment on one surface with a structure by using oxygen under the condition of 100W for 1min, performing hydrophobic modification on the surface of the structure by using heptadecafluorodecyltriethoxysilane steam at 120 ℃ for 2h, and performing renaturation on the modified reverse template by using polydimethylsiloxane to obtain a surface with the same structure as the basic model;
(4) And performing hydrophilic modification on the surface of the obtained structure by using an oxygen plasma instrument for discharge treatment, wherein the used gas is oxygen, the discharge power is 100W, and the treatment time is 1min.
In this embodiment, the prepared surface protrusion structure has the following appearance: the bottom is a regular polygon with the number of sides of 6, and the top is gradually changed into a round bulge. The sizes of the prepared convex structures are that the diameter of the circumscribed circle of the regular hexagon is 150 mu m, the height of the convex is 150 mu m, and the space between the convex structures is 10 mu m. The prepared micro-bump structure also has a secondary stepped structure, and the average layer height is 10 mu m.
In this example, after the surface is subjected to hydrophilic treatment by an oxygen plasma instrument, and the surface is placed in air at room temperature for 3 hours, the intrinsic contact angle of the surface is raised to about 60 °, and the resulting structure surface still has super-spreading performance.
1 μ L of deionized water was quickly spread as a layer on the surface of the structure obtained in this exampleHomogeneous liquid film, reaching maximum spreading area within 2.6s, about 0.4cm 2 。
Claims (6)
1. A bionic super-spreading surface is characterized in that a micron convex structure is arranged on the surface, and the convex structure is regularly arranged on the surface in a honeycomb structure manner; the bottom surface of the convex structure is a polygon with the number of sides not less than 6, and the bottom surface of the convex structure is finally circular along with the increase of the number of sides; the diameter of the cross section of the structure is gradually reduced from the bottom to the top of the protruding structure, namely the distance between two adjacent protrusions is gradually increased from the bottom to the top; the diameter range of the circumscribed circle of the bottom shape of the protruding structure is 1-500 mu m, the distance between the edges of the bottom of the micron protruding structure is not more than 1/4 of the diameter of the circumscribed circle of the bottom structure, and the ratio range of the diameter of the circumscribed circle of the bottom shape of the protruding structure to the height of the protruding structure is 1/3~3; the material of the surface is a material with an intrinsic contact angle of less than or equal to 60 degrees or a material which is subjected to hydrophilic modification to reduce the contact angle to be less than 60 degrees.
2. The bionic superspreading surface according to claim 1, wherein the material with intrinsic contact angle less than or equal to 60 ° is polyvinyl alcohol, polyamide or metallic aluminum; the material which is subjected to hydrophilic modification to reduce the contact angle to be below 60 degrees is polyurethane, polydimethylsiloxane or polystyrene.
3. The bionic superspreading surface according to claim 1 or 2, wherein the micro-protrusion structure further comprises a secondary structure, and the secondary structure is a micro-step structure, a nano-bead structure or a combination of the micro-step structure and the nano-bead structure.
4. The method for preparing the bionic super spreading surface according to claim 1, which is characterized by comprising the following steps:
(1) Preparing a base model of the bionic surface, and performing complex shape on the model to obtain a counter template or directly preparing the counter template;
(2) The surface material is different from the reverse template, and the reverse template is directly subjected to complex forming to obtain a surface structure; if the materials of the surface material and the reverse template are the same, after the reverse template is subjected to hydrophobic modification, the modified reverse template is subjected to reshaping by using the surface material to obtain a surface structure with the same structure as the basic model;
(3) If the intrinsic contact angle of the surface structure obtained in the step (2) is less than or equal to 60 degrees, the surface structure is a final surface structure;
and (3) if the intrinsic contact angle of the surface structure obtained in the step (2) is larger than 60 degrees, carrying out hydrophilic modification to obtain the final surface structure.
5. The method for preparing the bionic super-spreading surface according to claim 4, wherein the step (3) of hydrophilic modification is to treat the surface structure of the step (2) by an oxygen plasma instrument, modify stable hydrophilic groups on the surface structure of the step (2) or spray a hydrophilic coating on the surface structure of the step (2).
6. The method for preparing the bionic super spreading surface according to claim 5, wherein the step of modifying the stable hydrophilic group on the surface structure of the step (2) is to graft an aminosilane coupling agent on the surface structure of the step (2); spraying the hydrophilic coating on the surface structure in the step (2) refers to spraying hydrophilic titanium dioxide sol on the surface structure in the step (2).
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| CN108889575A (en) * | 2018-07-06 | 2018-11-27 | 华北电力大学 | A kind of alternate surface construction method of Metal Substrate hydrophobe striped |
| WO2020060497A2 (en) * | 2018-09-20 | 2020-03-26 | National Science And Technology Development Agency | Materials with pattern array for antifouling surface |
| CN112126101A (en) * | 2020-09-22 | 2020-12-25 | 湖北大学 | Preparation method of super-smooth surface with anisotropic hydrophilicity |
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| CN108889575A (en) * | 2018-07-06 | 2018-11-27 | 华北电力大学 | A kind of alternate surface construction method of Metal Substrate hydrophobe striped |
| WO2020060497A2 (en) * | 2018-09-20 | 2020-03-26 | National Science And Technology Development Agency | Materials with pattern array for antifouling surface |
| CN112126101A (en) * | 2020-09-22 | 2020-12-25 | 湖北大学 | Preparation method of super-smooth surface with anisotropic hydrophilicity |
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