CN114014260A - Friction-resistant super-hydrophobic surface material and preparation method thereof - Google Patents
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- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
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Abstract
The invention discloses a friction-resistant super-hydrophobic surface material and a preparation method thereof, wherein the friction-resistant super-hydrophobic surface material comprises the following steps: providing a substrate material, and processing a groove array with a micro-nano structure on the substrate material by using laser; covering a layer of polytetrafluoroethylene film on the surface of the processed substrate material, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along a first direction by using laser; removing the polytetrafluoroethylene film, covering a layer of new polytetrafluoroethylene film on the surface of the substrate material, and embedding new polytetrafluoroethylene particles into the groove array again along a second direction by using laser; and removing the new polytetrafluoroethylene film to obtain the friction-resistant super-hydrophobic surface material. According to the invention, the polytetrafluoroethylene particles with micro-nano sizes are embedded into the groove array by using laser, so that the surface of the substrate material has super-hydrophobic characteristics, and still has higher hydrophobicity after friction, and the method is simple to operate, free from environmental pollution, wide in applicability and suitable for various substrates.
Description
Technical Field
The invention relates to the field of surface treatment and laser processing, in particular to a friction-resistant super-hydrophobic surface material and a preparation method thereof.
Background
The super-hydrophobic surface generally refers to a surface with a contact angle with water larger than 150 degrees and a roll-off angle smaller than 10 degrees, and the research on the super-hydrophobic performance of the micro-structural surface has been long, and originally originated from the discovery of lotus effect of the biological surface, and the basic research on the hydrophobicity of various biological surfaces shows that a plurality of biological surfaces have a hierarchical structure combining micro-scale and nano-scale, and the micro-nano-scale combined double-layer or multi-layer composite rough structure is the main reason for the super-hydrophobic performance of a plurality of biological surfaces.
The super-hydrophobic surface has extremely wide application prospect in industrial and agricultural production and daily life of people, the super-hydrophobic surface prepared on a substrate material is more and more concerned, people desire to apply the super-hydrophobic performance to the industrial and agricultural production, and the obtained durable super-hydrophobic surface has important significance in self-cleaning, anti-icing and frost-inhibiting directions and the like. At present, there are many scholars and subjects who work on how to obtain a stable and durable Super-hydrophobic surface, according to the technical contents disclosed in the article of "Super-hydrophobic Co3O4-loaded hydrophobic foam with correction-property preparation by combination of hydro-synthesis and PFAS modification", Liu et al obtain a Super-hydrophobic surface by a hydro-thermal method, according to the technical contents disclosed in the article of "Large-scale surface of durable and robust Super-hydrophobic coating with excellent correction-property modification and preparation, Li et al obtain a Super-hydrophobic coating by a chemical synthesis method, but such methods have the problems of Large environmental pollution, complex process, long time, excessive cost and the like.
In view of the above, there is a need for a friction-resistant superhydrophobic surface material and a method for preparing the same to solve or at least alleviate the above-mentioned drawbacks.
Disclosure of Invention
The invention mainly aims to provide a friction-resistant super-hydrophobic surface material and a preparation method thereof, and aims to solve the problems of great environmental pollution, complex process, long time consumption and high cost of the existing method for preparing the super-hydrophobic surface. In order to achieve the aim, the invention provides a preparation method of a friction-resistant super-hydrophobic surface material, which comprises the following steps:
s1, providing a substrate material, and processing a groove array with a micro-nano structure on the substrate material by using laser, wherein the groove array is processed at least along two directions, the two directions comprise a first direction and a second direction, a first stripe interval is arranged between first grooves arranged along the first direction, and a second stripe interval is arranged between second grooves arranged along the second direction;
s2, covering a layer of polytetrafluoroethylene film on the surface of the processed substrate material, and scanning the surface of the polytetrafluoroethylene film by using laser along the first direction in a laser scanning mode smaller than the first stripe interval so as to embed polytetrafluoroethylene particles with micro-nano sizes into the groove array;
s3, removing the polytetrafluoroethylene film processed in the step S2, covering a new polytetrafluoroethylene film on the surface of the substrate material, and scanning the surface of the new polytetrafluoroethylene film by using laser along the second direction in a laser scanning mode smaller than the second stripe interval so as to embed the polytetrafluoroethylene particles with the micro-nano size into the groove array again;
s4, removing the new polytetrafluoroethylene film processed in the step S3 to obtain the friction-resistant super-hydrophobic surface material.
Preferably, the first direction is perpendicular to the second direction, and the groove array is a "#" shaped array.
Preferably, the substrate material is one selected from quartz glass, silicon wafer, or stainless steel.
Preferably, the substrate material is quartz glass, and in step S1, the laser has a processing stripe pitch of 100 μm and a processing speed of 0.5 mm/S.
Preferably, in each of the step S2 and the step S3, the processing stripe pitch of the laser is 50 μm, and the processing speed of the laser is 100 mm/S.
Preferably, the laser adopts a femtosecond laser, and the processing is carried out by a laser direct writing mode.
Preferably, the wavelength of the femtosecond laser is 1030nm, the pulse duration of the femtosecond laser is 330-370 fs, and the repetition frequency of the femtosecond laser is 80-120 KHz.
Preferably, the polytetrafluoroethylene film has a thickness of 25 to 35 μm.
Preferably, the polytetrafluoroethylene film has a thickness of 30 μm.
The invention also provides a friction-resistant super-hydrophobic surface material which is prepared by the preparation method.
Compared with the prior art, the friction-resistant super-hydrophobic surface material and the preparation method provided by the invention have the following beneficial effects:
the invention provides a friction-resistant super-hydrophobic surface material and a preparation method thereof, wherein the friction-resistant super-hydrophobic surface material comprises the following steps: providing a substrate material, and processing a groove array with a micro-nano structure on the substrate material by using laser; covering a layer of polytetrafluoroethylene film on the surface of the processed substrate material, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along a first direction by using laser; removing the polytetrafluoroethylene film, covering a layer of new polytetrafluoroethylene film on the surface of the substrate material, and embedding new polytetrafluoroethylene particles into the groove array again along a second direction by using laser; and removing the new polytetrafluoroethylene film to obtain the friction-resistant super-hydrophobic surface material. According to the invention, the groove and the bulge structures on the surface of the substrate material are constructed by using laser, and the polytetrafluoroethylene particles with micro-nano sizes are embedded into the groove array by using laser, so that the surface of the substrate material has super-hydrophobic characteristics, and the surface of the substrate material still has higher hydrophobicity after friction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method of making a friction-tolerant superhydrophobic surface material in one embodiment of the invention;
FIG. 2 is a scanning electron microscope image of the processed superhydrophobic quartz glass surface in the first embodiment of the invention, wherein a is a 500 times magnified scanning electron microscope image of the superhydrophobic quartz glass surface, and b is a 2000 times magnified scanning electron microscope image of the superhydrophobic quartz glass surface;
FIG. 3 is a 10000 times magnified SEM image of the surface of the processed superhydrophobic quartz glass in the first embodiment of the invention, wherein a is the 10000 times magnified SEM image of the groove on the surface of the superhydrophobic quartz glass, and b is the 10000 times magnified SEM image of the protrusion on the surface of the superhydrophobic quartz glass;
fig. 4 is a scanning electron microscope image of the rubbed super-hydrophobic quartz glass surface in the first embodiment of the present invention, wherein a is a 500 times magnified scanning electron microscope image of the rubbed super-hydrophobic quartz glass surface, and b is a 2000 times magnified scanning electron microscope image of the rubbed super-hydrophobic quartz glass surface;
fig. 5 is a scanning electron microscope image of the rubbed super-hydrophobic quartz glass surface in the first embodiment of the present invention, wherein a is a 10000 times enlarged scanning electron microscope image of the rubbed super-hydrophobic quartz glass surface groove, and b is a 10000 times enlarged scanning electron microscope image of the rubbed super-hydrophobic quartz glass surface protrusion;
fig. 6 is a schematic view of a water contact angle of the surface of the super-hydrophobic quartz glass in the first embodiment of the present invention, where a is a schematic view of a water contact angle of the processed super-hydrophobic quartz glass surface, and b is a schematic view of a water contact angle of the super-hydrophobic quartz glass surface after friction treatment;
fig. 7 is a schematic view of a water contact angle of the surface of a super-hydrophobic silicon wafer in the second embodiment of the present invention, where a is a schematic view of a water contact angle of the surface of a processed super-hydrophobic silicon wafer, and b is a schematic view of a water contact angle of the surface of a super-hydrophobic silicon wafer after a rubbing treatment;
fig. 8 is a schematic diagram of a water contact angle of the superhydrophobic stainless steel surface in the third embodiment of the invention, where a is a schematic diagram of a water contact angle of the processed superhydrophobic stainless steel surface, and b is a schematic diagram of a water contact angle of the superhydrophobic stainless steel surface after a rubbing treatment.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Referring to the attached drawings 1-8, the invention provides a preparation method of a friction-resistant super-hydrophobic surface material, which comprises the following steps:
s1, providing a substrate material, and processing a groove array with a micro-nano structure on the substrate material by using laser, wherein the groove array is processed at least along two directions, the two directions comprise a first direction and a second direction, a first stripe interval is arranged between first grooves arranged along the first direction, and a second stripe interval is arranged between second grooves arranged along the second direction;
s2, covering a layer of polytetrafluoroethylene film on the surface of the processed substrate material, and scanning the surface of the polytetrafluoroethylene film by using laser along the first direction in a laser scanning mode smaller than the first stripe interval so as to embed polytetrafluoroethylene particles with micro-nano sizes into the groove array;
s3, removing the polytetrafluoroethylene film processed in the step S2, covering a new polytetrafluoroethylene film on the surface of the substrate material, and scanning the surface of the new polytetrafluoroethylene film by using laser along the second direction in a laser scanning mode smaller than the second stripe interval so as to embed the polytetrafluoroethylene particles with the micro-nano size into the groove array again;
s4, removing the new polytetrafluoroethylene film processed in the step S3 to obtain the friction-resistant super-hydrophobic surface material.
Specifically, in a specific example, the thickness of the polytetrafluoroethylene film can be 25-35 μm, and in the present embodiment, a polytetrafluoroethylene film with a thickness of 30 μm is used.
It should be understood that the laser processing method includes various methods such as a pulse laser, a continuous laser, etc., the present embodiment uses one of pulse lasers, uses a femtosecond laser for processing, and processes by laser direct writing, the femtosecond laser processing has a small thermal influence on the periphery of the processing region, can process other types of materials that are difficult to process by laser, such as transparent materials, high-melting materials, thermal decomposers, and thermal deformation materials, etc., and can use a focused beam for internal processing in a controlled depth direction.
In detail, the parameters of the femtosecond laser processing can be adjusted according to the selected substrate material, and in this embodiment, the following ranges can be selected: the wavelength is 1030nm, the pulse duration is 330-370 fs, the repetition frequency is 80-120 KHz, the processing speed is 0.5-100 mm/s, and the processing interval is 50-120 μm.
In step S1, specifically, the substrate material may be one or more of quartz glass, a silicon wafer, and stainless steel, a groove array with a micro-nano structure is processed on the substrate material at least along two directions by using laser, and a grid structure is constructed on the substrate material, so that the polytetrafluoroethylene particles with the micro-nano size may be distributed on the surface of the substrate material and in the grooves.
It should be noted that the two directions mean that the laser can process on the substrate material along any two directions, and the processing distance can be adjusted according to the actually selected substrate material, and the first grooves processed along the first direction have a first stripe distance therebetween, and the second grooves processed along the second direction have a second stripe distance therebetween. In this embodiment, the substrate material is made of quartz glass, the pitch of the processing stripes of the laser is set to 100 μm, the processing speed of the laser is set to 0.5mm/s, the first direction is set to the horizontal direction, the second direction is set to the vertical direction, the first direction and the second direction are perpendicular to each other, and the groove array is constructed as a "#" shaped array.
In steps S2 and S3, the processing directions respectively correspond to the first direction and the second direction in step S1, and the processing stripe pitch is smaller than the processing stripe pitch in step S1, so that the polytetrafluoroethylene particles having the micro-nano size can be more uniformly distributed in the groove and protrusion structures of the base material. Referring to fig. 2 and 3 together, it can be seen that the groove array has a micro-nano structure, the micro-nano structure includes a plurality of groove and protrusion structures, and each of the groove and protrusion structures is composed of nano particles with a size of tens to hundreds of nanometers, and exhibits a micro-scale porous structure. Also in the example in which the above-described substrate material is quartz glass, in steps S2 and S3, the processing fringe pitch of the laser light is set to 50 μm, and the processing speed of the laser light is set to 100 mm/S.
Removing the new polytetrafluoroethylene film processed in the step S3 to obtain a friction-resistant super-hydrophobic surface material, wherein the grooves and the raised structures of the substrate material are covered with polytetrafluoroethylene particles with micro-nano sizes, the surface of the substrate material shows super-hydrophobic characteristics, and after the surface of the substrate material is subjected to friction treatment, the raised structures on the surface of the substrate material are worn, and part of the polytetrafluoroethylene particles attached to the raised structures disappear, but the raised structures on the surface of the substrate material can well protect the polytetrafluoroethylene particles in the grooves, so that the surface of the substrate material still shows good hydrophobicity. Referring to fig. 4 and 5 together, it can be seen that the surface of the substrate material is abraded to a certain extent after the surface is subjected to the rubbing treatment, and under the condition that the magnification of the groove structure and the protrusion structure is 10000 times, it can be seen that the protrusion structure is abraded to a large extent, but the abrasion of the groove structure is small, that is, the polytetrafluoroethylene particles in the groove are protected, and the surface of the substrate material still shows good hydrophobicity.
The results show that the grooves and the protruding structures on the surface of the substrate material are constructed by using laser, and the polytetrafluoroethylene particles with micro-nano sizes are embedded into the groove array by using the laser, so that the surface of the substrate material has super-hydrophobic characteristics, and the surface of the substrate material still has higher hydrophobicity after friction.
The invention also provides a friction-resistant super-hydrophobic surface material which is prepared by the preparation method.
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) The substrate material is quartz glass, the water contact angle of the quartz glass is 31 degrees, and the thickness of the polytetrafluoroethylene film is 30 micrometers.
(2) Processing a groove array with a micro-nano structure processed in the horizontal direction and the vertical direction on quartz glass by using femtosecond laser; wherein the laser processing parameters are as follows: the distance between the processing stripes is 100 mu m, the processing speed is 0.5mm/s, the repetition frequency is 100KHz, the pulse duration is 350fs, the wavelength is 1035nm, and the output is 100 percent;
(3) covering a layer of polytetrafluoroethylene film on the surface of the processed quartz glass, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along the horizontal direction by using femtosecond laser; removing the processed polytetrafluoroethylene film, covering a layer of new polytetrafluoroethylene film on the surface of quartz glass, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along the vertical direction by using femtosecond laser; wherein the laser processing parameters are as follows: the distance between the processing stripes is 50 μm, the processing speed is 100mm/s, the repetition frequency is 100KHz, the pulse duration is 350fs, the wavelength is 1035nm, and the output is 80%;
(4) removing the new polytetrafluoroethylene film after processing to obtain the quartz glass with the surface friction-resistant and super-hydrophobic, wherein the water contact angle of the quartz glass is 159 degrees, the quartz glass is loaded with 100 grams and rubbed on 200-mesh sand paper for 10 centimeters, and the water contact angle of the rubbed quartz glass is 154 degrees.
As shown in fig. 2 and 3, it can be seen that the surface of the superhydrophobic quartz glass has a groove array of a micro-nano structure, the micro-nano structure includes a plurality of groove and protrusion structures, and the groove and protrusion structures are composed of nanoparticles with a size of tens to hundreds of nanometers and present a micron-sized porous structure; as shown in fig. 4 and 5, it can be seen from fig. 4 and 5 that the surface of the quartz glass is abraded to a certain extent after being rubbed, and the concave and convex structures are enlarged by 10000 times, so that the convex structure is abraded to a large extent, but the concave structure is abraded to a small extent; as shown in fig. 6, fig. 6 is a schematic diagram showing a comparison of water contact angles before and after rubbing of the surface of the super-hydrophobic quartz glass, in which the water contact angle in fig. a is 159 degrees and the water contact angle in fig. b is 154 degrees, and the change in the water contact angle is small.
Example 2
(1) The substrate material is a silicon wafer, the water contact angle of the silicon wafer is 26 degrees, and the thickness of the polytetrafluoroethylene film is 30 micrometers.
(2) Processing a groove array with a micro-nano structure on a silicon wafer along the horizontal direction and the vertical direction by using femtosecond laser; wherein the laser processing parameters are as follows: the distance between the processing stripes is 100 mu m, the processing speed is 50mm/s, the repetition frequency is 100KHz, the pulse duration is 350fs, the wavelength is 1035nm, and the output is 70 percent;
(3) covering a layer of polytetrafluoroethylene film on the surface of the processed silicon wafer, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along the horizontal direction by using femtosecond laser; removing the processed polytetrafluoroethylene film, covering a layer of new polytetrafluoroethylene film on the surface of the silicon wafer, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along the vertical direction by using femtosecond laser; wherein the laser processing parameters are as follows: the distance between the processing stripes is 50 μm, the processing speed is 100mm/s, the repetition frequency is 100KHz, the pulse duration is 350fs, the wavelength is 1035nm, and the output is 80%;
(4) removing the processed new polytetrafluoroethylene film to obtain a silicon wafer with a friction-resistant and super-hydrophobic surface, wherein the water contact angle of the silicon wafer is 168 degrees, the silicon wafer is loaded with 100 g and rubbed on 200-mesh sand paper for 10 cm, and the water contact angle of the rubbed silicon wafer is 164 degrees.
As shown in fig. 7, fig. 7 is a comparison graph of water contact angles before and after rubbing of the surface of the superhydrophobic silicon wafer, where the water contact angle in fig. a is 168 degrees, the water contact angle in fig. b is 164 degrees, and the change of the water contact angle is small.
Example 3
(1) The substrate material is stainless steel, the water contact angle of the stainless steel is 31 degrees, and the thickness of the polytetrafluoroethylene film is 30 micrometers.
(2) Processing a groove array with a micro-nano structure on stainless steel along the horizontal direction and the vertical direction by using femtosecond laser; wherein the laser processing parameters are as follows: the distance between the processing stripes is 100 mu m, the processing speed is 5mm/s, the repetition frequency is 100KHz, the pulse duration is 350fs, the wavelength is 1035nm, and the output is 100 percent;
(3) covering a layer of polytetrafluoroethylene film on the surface of the processed stainless steel, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along the horizontal direction by using femtosecond laser; removing the processed polytetrafluoroethylene film, covering a layer of new polytetrafluoroethylene film on the surface of the stainless steel, and embedding polytetrafluoroethylene particles with micro-nano sizes into the groove array along the vertical direction by using femtosecond laser; wherein the laser processing parameters are as follows: the distance between the processing stripes is 50 μm, the processing speed is 100mm/s, the repetition frequency is 100KHz, the pulse duration is 350fs, the wavelength is 1035nm, and the output is 80%;
(4) removing the processed new polytetrafluoroethylene film to obtain the stainless steel with the surface friction-resistant and super-hydrophobic, wherein the water contact angle of the stainless steel is 157 degrees, the stainless steel is loaded with 100 g and rubbed on 200-mesh sand paper for 10 cm, and the water contact angle of the stainless steel after being rubbed is 138 degrees.
As shown in fig. 8, fig. 8 is a schematic diagram comparing water contact angles before and after rubbing of the surface of the super-hydrophobic stainless steel, where the water contact angle in fig. a is 168 degrees, the water contact angle in fig. b is 164 degrees, and the change of the water contact angle is small.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a friction-resistant super-hydrophobic surface material is characterized by comprising the following steps:
s1, providing a substrate material, and processing a groove array with a micro-nano structure on the substrate material by using laser, wherein the groove array is processed at least along two directions, the two directions comprise a first direction and a second direction, a first stripe interval is arranged between first grooves arranged along the first direction, and a second stripe interval is arranged between second grooves arranged along the second direction;
s2, covering a layer of polytetrafluoroethylene film on the surface of the processed substrate material, and scanning the surface of the polytetrafluoroethylene film by using laser along the first direction in a laser scanning mode smaller than the first stripe interval so as to embed polytetrafluoroethylene particles with micro-nano sizes into the groove array;
s3, removing the polytetrafluoroethylene film processed in the step S2, covering a new polytetrafluoroethylene film on the surface of the substrate material, and scanning the surface of the new polytetrafluoroethylene film by using laser along the second direction in a laser scanning mode smaller than the second stripe interval so as to embed the polytetrafluoroethylene particles with the micro-nano size into the groove array again;
s4, removing the new polytetrafluoroethylene film processed in the step S3 to obtain the friction-resistant super-hydrophobic surface material.
2. The method of claim 1, wherein the first direction is perpendicular to the second direction, and the groove array is a "#" shaped array.
3. The method according to claim 1, wherein the substrate material is one selected from quartz glass, silicon wafer and stainless steel.
4. The method according to claim 3, wherein the substrate material is quartz glass, the pitch of the processing stripes of the laser is 100 μm, and the processing speed of the laser is 0.5mm/S in step S1.
5. The method of claim 4, wherein the laser processing is performed at a pitch of 50 μm in each of the steps S2 and S3, and the laser processing is performed at a speed of 100 mm/S.
6. The method for preparing the friction-resistant superhydrophobic surface material according to claim 1, wherein the laser is femtosecond laser and is processed by direct laser writing.
7. The method for preparing the friction-resistant superhydrophobic surface material according to claim 7, wherein the wavelength of the femtosecond laser is 1030nm, the pulse duration of the femtosecond laser is 330-370 fs, and the repetition frequency of the femtosecond laser is 80-120 KHz.
8. The method of preparing a rub-resistant superhydrophobic surface material of claim 1, wherein the polytetrafluoroethylene film has a thickness of 25-35 μ ι η.
9. The method of claim 8, wherein the polytetrafluoroethylene film has a thickness of 30 μm.
10. A friction-resistant superhydrophobic surface material, characterized by being prepared by the preparation method according to any one of claims 1-9.
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| CN116272376A (en) * | 2023-03-10 | 2023-06-23 | 中南大学 | Super-hydrophobic film for membrane distillation, preparation, application and device |
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