CN115926348B - Underwater super-strong cyclic adhesion material and preparation method and application thereof - Google Patents
Underwater super-strong cyclic adhesion material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an underwater super-strong cyclic adhesion material, a preparation method and application thereof, wherein the underwater super-strong cyclic adhesion material has the following structure: the adhesion surface is the combination of the hole-shaped part and the plane part; the top surface and the periphery are of a sealing structure; inside is a vertically oriented hole channel structure. The underwater super-strong cyclic adhesion material can be applied to air, water, silicone oil and other liquid environments, and has excellent cyclic adhesion performance on glass, copper, polytetrafluoroethylene and other substrates. Therefore, the underwater super-strong circulating adhesive material disclosed by the invention has strong universality and can be widely applied to the fields of underwater crawling robots, underwater grabbing robots and the like.
Description
Technical Field
The invention belongs to the technical field of underwater adhesive materials, and particularly relates to an underwater super-strong circulating adhesive material, and a preparation method and application thereof.
Background
An underwater robot needs an adhesive material which can be stably adhered and has excellent cycle performance in the process of performing underwater operations such as crawling and grabbing. At present, researches on underwater adhesive materials are continuously advanced, and the underwater adhesive materials can be divided into two types of glue type adhesive materials and adhesive tape type adhesive materials according to the physical forms of the adhesive materials. The glue type adhesive material is in a liquid form, and increases cohesion through a curing process to realize strong underwater adhesion. However, the glue adhesive material has the defects of long curing time, incapability of recycling and the like, and is generally used as underwater permanent glue. The adhesive tape type adhesive material is in a solid form, the adhesion process is simple, and the adhesive tape type adhesive material can be directly adhered to a substrate by pressing.
Adhesive tape-like adhesive materials can be classified into hydrogel and bionic micro-nano arrays. The hydrogel material realizes underwater adhesion through the actions of hydrogen bond or electrostatic force, and can realize stronger underwater adhesion, but has poorer cycle performance (less than or equal to 50 times). For example, professor Xu Xiaofeng to the university of ocean in China and Petri Murto doctor in Cambridge, england synthesized a series of polymer gels that exhibited efficient and stable adhesion on the surface of various underwater objects, with adhesion strengths as high as 840kPa, but which could achieve only 5-cycle adhesion. The reason for the poor cycle performance of hydrogel materials is that their structure is easily broken during the adhesion-desorption process. The bionic micro-nano array firstly eliminates water at an interface through a bionic micro-nano structure, and further realizes underwater adhesion through the actions of suction force, capillary force or Van der Waals force and the like. The bionic micro-nano array has good circulation performance, but has lower adhesive strength. For example, changhun Pang group reported a study of an octopus-like suction cup array underwater adhesive material on Nature. The material can realize the underwater adhesion circulation performance of 10000 times, but the underwater adhesion strength is only 40kPa. The reason that the bionic micro-nano array can realize high cycle performance is that the structure is not destroyed in the adhesion-desorption cycle, but the drainage efficiency is poor, and the preparation technology of the material limits the breakthrough of the material in high adhesion performance.
For the underwater robot needing long-time and repeated operation, the circulation performance of the hydrogel material and the adhesion performance of the bionic micro-nano array can not meet the use requirements. In order to meet the operation requirement of the underwater robot, an underwater super-strong circulating adhesive material is needed, and super-strong circulating times are defined as circulating times which are more than 100 times. In recent years, underwater adhesive materials based on suction effect have received attention because of their structural stability in multiple adhesion-desorption cycles to achieve high cycle performance. The invention aims to design a structure capable of realizing ultra-high cycle performance based on suction effect, and improves the adhesion performance through the structural design of the material, and finally develops the underwater ultra-high cycle adhesion material with high adhesion strength and high cycle performance.
Disclosure of Invention
In response to the above-mentioned deficiencies or improvements of the prior art, the present invention provides an underwater super-strong cyclic adhesive material. The invention prepares the underwater super-strong circulating adhesive material with the vertical directional pore channel and the surface pore structure by using the template material with the vertical directional three-dimensional structure and the high polymer material. The preparation method provided can realize the accurate regulation and control of the adhesion performance of the material, and successfully develop the underwater super-strong cyclic adhesion material with high adhesion strength and high cyclic performance. The technical problem that the high adhesive strength and the high cycle performance of the underwater adhesive material are difficult to achieve is solved, and the application requirements of the fields of underwater robots and the like are met.
In order to achieve the above object, according to one aspect of the present invention, there is provided an underwater super-strong circulating adhesive material having the structure:
(1) The adhesion surface is the combination of the hole-shaped part and the plane part;
(2) The top surface and the periphery are of a sealing structure;
(3) Inside is a vertically oriented hole channel structure.
The top surface refers to the surface opposite to the adhesion surface.
Further, in the structure of the underwater super-strong circulating adhesive material, the hole-shaped part and the plane part of the adhesive surface can respectively generate suction force action under the action of pre-pressure, the plane part of the adhesive surface can generate capillary force action, and the combination of the two can realize underwater adhesive performance; the sealing structure on the top surface and the periphery is a precondition for generating suction force. When pulling force is applied to the adhesive material to gradually separate from the substrate, suction force and capillary force are destroyed to realize desorption, and the vertical orientation hole channel structure provides good mechanical property to ensure that the structure of the material is not destroyed in the process of multiple adhesion-desorption, thereby realizing super-strong cycle performance.
Further, the ratio of the area of the hole-shaped part of the adhesion surface to the total area is in the range of 20% -90%.
Further, the preparation method for realizing the special structure of the underwater super-strong circulating adhesive material comprises the following steps:
(1) Preparing a three-dimensional structure material with vertical orientation, and taking the three-dimensional structure material as a template material;
(2) The polymeric liquid is infiltrated into the template material and the template material is sealed by physical and/or chemical action.
Further, in the preparation method of the underwater super-strong cyclic adhesion material, the template material with the vertical orientation three-dimensional structure comprises a carbon nano tube forest, a silicon nano wire forest, graphene or MXene aerogel with a honeycomb structure and the like, and the structural parameters of the template material can be regulated and controlled.
Further, in the preparation method of the underwater super-strong cyclic adhesion material, the polymer liquid comprises polymer aqueous solutions such as polyvinyl alcohol aqueous solution, gelatin aqueous solution and the like, and polydimethylsiloxane, polyurethane acrylic ester and the like.
Further, in the preparation method of the underwater super-strong cyclic adhesion material, the types of the polymers in the polymer liquid are not limited to one type, and two or more types of polymers can be used simultaneously. The viscosity of the polymer liquid ranges from 1cs to 3000cs, so that the polymer liquid can penetrate into the template material with certain popularity.
Further, physical or/and chemical actions in the preparation method of the underwater super-strong cyclic adhesion material comprise solidification, a physical crosslinking method, a chemical crosslinking method and the like.
Further, the underwater cycle adhesive material is applicable not only to underwater environments but also to air environments and other liquid environments. Other liquids include electrolyte solutions such as NaCl solution, silicone oil, etc. The underwater circulation adhesive material can be applied to different types of substrates, including glass, stainless steel, copper, aluminum, polytetrafluoroethylene and the like.
Compared with the prior art, the underwater super-strong circulating adhesive material provided by the invention has the following main beneficial effects:
(1) The invention realizes the development of the underwater super-strong circulating adhesive material by designing a special structure with sealed top surface and periphery, a hole-shaped structure on the bottom surface (namely the adhesive surface) and a vertically oriented hole channel in the inside. The porous and planar structures of the adhesive surface may drain a portion of the water from the substrate when the material is immersed in water to contact and pre-stress the target substrate. After releasing the pre-pressure, the water remaining on the substrate is locked inside the aspirated sample. Under the condition that the top surface and the periphery of the sample are sealed, pressure difference exists between the inside and the outside of the hole-shaped structure of the adhesion surface, so that suction force is generated. The planar structure of the adhesive surface generates capillary force due to the presence of the three-phase medium. The combination of suction and capillary action can achieve high adhesion properties. In addition, the good mechanical property of the sample ensures that the structure of the sample is not destroyed in the adhesion-desorption cycle, thereby realizing high cycle performance.
(2) According to the preparation method of the underwater super-strong circulating adhesive material, the pore structure parameters of the material can be adjusted by changing the parameters of the template material and the polymer liquid during preparation, and finally, the accurate regulation and control of the material performance can be realized, so that the underwater super-strong circulating adhesive material is suitable for different application scenes. Specifically, the area ratio of the adhesion surface hole structure is an important parameter affecting the adhesion performance of the material, and the controllable adjustment of the underwater adhesion performance of the material can be realized by adjusting the area ratio of the hole structure.
(3) The underwater super-strong cyclic adhesive material provided by the invention realizes high adhesive strength and high cyclic performance. In particular, the developed material has an adhesion strength of up to 210kPa on an underwater glass substrate, and its adhesion performance can be kept stable in 30000 adhesion-desorption times. The adhesive strength and the cycle performance of the material under water are obviously superior to those of the underwater super-strong cycle adhesive material in other current researches. In addition, the underwater super-strong cyclic adhesion material can be applied to air and various liquid environments such as water, silicone oil and the like, and has excellent cyclic adhesion performance on substrates such as glass, copper, polytetrafluoroethylene and the like. Therefore, the underwater super-strong circulating adhesive material disclosed by the invention has strong universality and can be widely applied to the fields of underwater crawling robots, underwater grabbing robots and the like.
(4) The underwater super-strong circulating adhesive material provided by the invention has the advantages of simple preparation process, high efficiency and prospect of industrial production and large-scale popularization and application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
fig. 1 is a schematic structural view of an underwater super-strong circulating adhesive material provided by the invention.
FIG. 2 is a schematic illustration of the preparation flow of example 1.
FIG. 3 is a scanning electron microscope image of the adhesive material obtained in example 1.
FIG. 4 shows the adhesion properties in water of the different structural parameters of the adhesive material obtained in example 1.
FIG. 5 shows the cycle performance of the adhesive material obtained in example 1 in water.
FIG. 6 adhesion properties of the adhesion material obtained in example 1 on different substrates in water.
FIG. 7 shows the adhesion properties of the adhesive material obtained in example 1 in air, water, ethanol, silicone oil.
FIG. 8 is an underwater cycle adhesion property of the adhesive material obtained in example 2.
FIG. 9 shows the underwater cycle adhesion properties of the adhesion material obtained in example 3.
FIG. 10 is an underwater cycle adhesion property of the adhesive material obtained in example 4.
FIG. 11 shows the underwater cycle adhesion properties of the adhesion material obtained in example 5.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Referring to fig. 1, the structure of the underwater super-strong circulating adhesive material provided by the invention is that (1) an adhesive surface (namely a bottom surface) is the combination of a hole-shaped part and a plane part; (2) the top surface and the periphery are sealed; (3) inside is a vertically oriented hole channel structure. Wherein the hole-shaped portion and the plane portion of the adhesion surface can generate suction force and capillary force to form underwater strong adhesion; tightness of the top and periphery is a precondition for the generation of suction. The internal vertically oriented pore channel structure provides good mechanical properties to achieve underwater super-strong cycling performance of the material.
The preparation method for forming the structure comprises the following steps:
(1) Preparing a three-dimensional structure material with vertical orientation, and taking the three-dimensional structure material as a template material. (2) The polymer liquid is permeated into the template material, and the template material is sealed by one or more of physical crosslinking, chemical crosslinking and curing.
The structure of the underwater super-strong circulating adhesive material provided by the invention can be adjusted by changing parameters in the preparation process, and finally the underwater adhesive material with high adhesive property and high circulating property can be obtained.
Example 1:
the embodiment of the invention provides a preparation method of an underwater super-strong circulating adhesive material, which comprises the following steps: preparing a carbon nano tube forest as a template material, and selecting a polyvinyl alcohol aqueous solution by using a high polymer liquid. The preparation flow is shown in fig. 2, and the detailed preparation steps are as follows:
(1) The method for preparing the carbon nanotube array as a template material by a water-assisted chemical vapor deposition method comprises the following specific steps: (1) and plating an aluminum buffer layer and an iron catalytic layer on the surface of the single-sided polished silicon wafer by a magnetron sputtering method. The aluminum buffer layer is sputtered by radio frequency reaction, high-purity argon gas is introduced into the sputtering process for 15sccm, the sputtering power is 200W, and the time is 60s. The iron catalyst layer adopts direct current sputtering, high-purity argon gas is introduced into the sputtering process for 12sccm, and the sputtering time is 45s. (2) And (3) placing the silicon wafer plated with the aluminum buffer layer and the iron catalyst layer into a three-inch tube furnace, and growing the carbon nanotube forest by a water-assisted chemical vapor deposition method. The total flow of the growth process gas is 2000sccm, wherein the content ratio of ethylene is 20%, the content ratio of hydrogen is 5% -20%, the content ratio of argon is 35% -50%, the content ratio of argon carrying water vapor is 25%, the growth temperature is 780 ℃, and the growth time is 150-800s. The forest density range of the prepared carbon nano tube is 5-40 mg/cm 3 The height range is 200-900 μm.
(2) An aqueous polyvinyl alcohol solution was prepared. Weighing a proper amount of polyvinyl alcohol, putting the polyvinyl alcohol into deionized water, and fully dissolving the polyvinyl alcohol by adopting a water bath heating method. The heating temperature is 85-90 ℃ and the heating time is about 30 minutes. In order to facilitate the penetration of the aqueous solution of polyvinyl alcohol into the forest of carbon nanotubes, the mass fraction of the aqueous solution of polyvinyl alcohol may be 1%, 3%, 5%, 7%, etc.
(3) Immersing the carbon nanotube forest obtained in the step (1) into the polyvinyl alcohol aqueous solution obtained in the step (2), heating the carbon nanotube forest in a water bath at 70 ℃ for about 20 minutes, and observing that bubbles are not generated on the surface of the carbon nanotube forest, thus completing the water bath.
(4) And (3) taking the carbon nanotube forest in the step (3) out of the polyvinyl alcohol aqueous solution, flushing the polyvinyl alcohol aqueous solution on the surface of the carbon nanotube forest with deionized water, and sucking the surface water by using dust-free paper.
(5) And (3) placing the carbon nanotube forest obtained in the step (4) in a freezing chamber at the temperature of minus 20 ℃, taking out the carbon nanotube forest after 24 hours, thawing the carbon nanotube forest to the room temperature, and placing the carbon nanotube forest in the freezing chamber. The polyvinyl alcohol in the carbon nano tube forest is subjected to physical crosslinking through repeated freezing-thawing operation, and finally the vertical directional pore channel and the surface pore structure are formed through the combined action of the carbon nano tube forest and the polyvinyl alcohol.
The carbon nanotube forest/polyvinyl alcohol sample with the area of the porous part on the adhesive surface accounting for 0.2-0.9 and the area size of 0.25cm can be prepared by the steps 2 . A scanning electron microscope image of the sample in which the area ratio of the pore structure was 0.22 is shown in fig. 3. The above samples were adhered to an underwater glass substrate under 5N pre-pressure, and the adhesion was measured by a digital tensile machine. The adhesive strength of the samples having the pore structure area ratios of 0.22, 0.35, 0.48, 0.67, and 0.88 were 48.8kPa,78.4kPa, 134.8kPa, 92.4kPa, and 66kPa, respectively, as shown in FIG. 4. The sample with the pore structure area ratio of 0.48 (namely 48%) was subjected to the cyclicity test on the underwater glass substrate under the 5N precompression, and the result is shown in fig. 5, wherein the adhesive strength of the sample after 32000 adhesion-desorption cycles is 87.6kPa, which indicates that the sample has the ultra-strong cyclic adhesion capability. To verify the applicability of the samples on various substrates under water, the samples were adhered to the substrates of glass, stainless steel, copper, aluminum and polytetrafluoroethylene under water under 15N pre-stress, and the adhesion strengths thereof were 210kPa, 200kPa, 175kPa, 190kPa and 160kPa, respectively, as shown in FIG. 6, by the digital display tensiometer test. In addition, in order to verify the applicability of the samples in different environments, the samples were adhered to a glass substrate by applying 15N pre-stress in air, ethanol and silicone oil environments, respectively, and the adhesion strengths thereof were 150kPa, 260kPa and 350kPa, respectively, as shown in FIG. 7, by a digital display tensile machine test.
Example 2:
the preparation method of the underwater super-strong circulating adhesive material provided in the embodiment 2 comprises the following steps: preparing a carbon nanotube forest as a template material, and selecting a polyvinyl alcohol-polydopamine mixed aqueous solution by using a high molecular liquid. The detailed preparation steps are as follows:
(1) The water-assisted chemical vapor deposition method is adopted to grow the carbon nanotube forest as a template material. The preparation method of the carbon nanotube forest in the embodiment 2 is the same as that of the embodiment 1, and the density of the carbon nanotube forest can be prepared to be 21mg/cm 3 The height is 550 μm.
(2) Preparing polydopamine suspension. 20mg of dopamine hydrochloride is weighed and placed in a reaction bottle A, and 10mL of deionized water is added for complete dissolution. 30mg of Tris was weighed and placed in a reaction flask B, and 10mL of deionized water was added for complete dissolution to prepare Tris liquid. Tris solution was added dropwise to the a solution, and the pH of the solution was tested with pH paper to prepare a mixed solution with ph=8.5. Adding a magnet into the reaction bottle A, placing the reaction bottle on a magnetic stirrer, and opening the bottle mouth. Oxygen is dissolved in the solution, and dopamine undergoes oxidation and self-polymerization. After 14 hours of reaction, deposition of polymerized dopamine particles was observed, and the preparation of the polydopamine suspension was successful.
(3) An aqueous polyvinyl alcohol solution was prepared. Weighing a proper amount of polyvinyl alcohol, putting the polyvinyl alcohol into deionized water, and fully dissolving the polyvinyl alcohol by adopting a water bath heating method. The heating temperature is 85-90 ℃ and the heating time is about 30 minutes. The mass fraction of the aqueous solution of the prepared polyvinyl alcohol may be 3%.
(4) Dispersing the polydopamine suspension obtained in the step (1) by adopting an ultrasonic pulverizer for about 30 min.
(5) And (3) mixing the polyvinyl alcohol aqueous solution obtained in the step (3) with the polydopamine suspension obtained in the step (4) to obtain a polyvinyl alcohol-polydopamine mixed solution. For example, 10ml of a polyvinyl alcohol aqueous solution having a mass fraction of 3% and 2ml of a polydopamine suspension having a concentration of 2mg/ml were mixed to obtain a polyvinyl alcohol-polydopamine mixed solution having a polyvinyl alcohol concentration of 2.5%.
(6) Immersing the carbon nanotube forest obtained in the step (1) into the polyvinyl alcohol-polydopamine mixed solution obtained in the step (5), heating the mixture in a water bath at 70 ℃ for about 20 minutes, and observing that bubbles are not generated on the surface of the carbon nanotube forest, thus completing the water bath.
(7) And (3) taking the carbon nanotube forest in the step (6) out of the polyvinyl alcohol-polydopamine mixed solution, flushing the polyvinyl alcohol-polydopamine mixed solution on the surface of the carbon nanotube forest with deionized water, and sucking the surface water by using dust-free paper.
(8) And (3) placing the carbon nanotube forest obtained in the step (7) in a freezing chamber, taking out the carbon nanotube forest after 24 hours, thawing the carbon nanotube forest to room temperature, and placing the carbon nanotube forest in the freezing chamber. And (3) performing physical crosslinking on the polyvinyl alcohol in the carbon nanotube forest through repeated freezing-thawing operation, and finally forming a vertical directional pore channel and a surface pore structure under the combined action of the carbon nanotube forest, the polyvinyl alcohol and the polydopamine.
The carbon nanotube forest/polyvinyl alcohol/polydopamine sample is prepared by the steps, and the area of the sample is 0.25cm 2 The cycle performance on a glass substrate in water under 5N pre-stress was tested and the results are shown in FIG. 8. After 30000 cycles of adhesion-desorption, the adhesion strength of the sample was 72.4kPa, which indicates that the sample prepared in this example 2 also had a super-strong cycle adhesion property.
Example 3:
the preparation method of the underwater super-strong circulating adhesive material provided in the embodiment 3 comprises the following steps: preparing a carbon nano tube forest as a template material, and selecting a gelatin aqueous solution as a high polymer liquid. The detailed steps are as follows:
(1) The water-assisted chemical vapor deposition method is adopted to grow the carbon nanotube forest as a template material. The preparation method of the carbon nanotube forest in the embodiment 3 is the same as that of the embodiment 1, and the density of the prepared carbon nanotube forest is 25mg/cm 3 The height is 650 μm.
(2) An aqueous gelatin solution was prepared. Weighing a proper amount of gelatin, putting the gelatin into deionized water, heating the gelatin in a water bath at 60 ℃ to dissolve the gelatin, and cooling the gelatin aqueous solution for standby, wherein the mass fraction of gelatin in the prepared gelatin aqueous solution is 3%.
(3) Immersing the carbon nanotube forest obtained in the step (1) into the gelatin aqueous solution obtained in the step (2), heating in a water bath at 40 ℃ for about 15 minutes, and taking out the carbon nanotube forest from the gelatin aqueous solution after no bubbles emerge from the surface of the carbon nanotube forest.
(4) And (3) washing the gelatin aqueous solution on the surface of the carbon nanotube forest obtained in the step (3) by deionized water, and then sucking water on the surface of the carbon nanotube forest by dust-free paper.
(5) And (3) placing the sample obtained in the step (4) in air or a low-temperature environment for about 1 hour, and curing gelatin in the carbon nanotube forest, so that the sample is successfully prepared.
The preparation method comprises the steps of preparing a carbon nano tube forest/gelatin sample, and adhering the sample to the surfaceSurface area of 0.25cm 2 The cycle performance on a glass substrate in water under 5N pre-stress was tested and the results are shown in FIG. 9. The sample after 8000 cycles of adhesion-desorption had an adhesion strength of 86.2kPa, indicating that the sample prepared in this example 3 had superior cycle adhesion properties.
Example 4:
the preparation method of the underwater super-strong circulating adhesive material provided in the embodiment 4 comprises the following steps: preparing graphene aerogel with a honeycomb structure as a template material, wherein the high polymer liquid is gelatin aqueous solution. The detailed steps are as follows:
(1) The preparation method of the graphene aerogel with the honeycomb structure comprises the following specific steps: (1) and weighing a proper amount of graphene oxide powder, dissolving in deionized water, and carrying out ultrasonic treatment for 5 hours to obtain a well-dispersed graphene oxide aqueous solution. (2) The graphene oxide aqueous solution was degassed in vacuo for 30 minutes. (3) Pouring the degassed graphene oxide aqueous solution into a pre-frozen mold, and then directionally freezing for at least 24 hours. (4) The sample obtained in step (3) was freeze-dried for 72 hours at-70℃and 0.1Pa. Finally preparing the graphene aerogel with the honeycomb structure.
(2) An aqueous gelatin solution was prepared. Weighing a proper amount of gelatin, putting the gelatin into deionized water, heating the gelatin in a water bath at 60 ℃ to dissolve the gelatin, and cooling the gelatin aqueous solution for standby, wherein the mass fraction range of gelatin in the prepared gelatin aqueous solution can be 3%.
(3) Immersing the sample obtained in the step (1) in the gelatin water solution obtained in the step (2), and taking out the sample after at least 1 hour.
(4) Washing the sample taken out in the step (3) with deionized water, washing the gelatin water solution on the surface of the sample, and sucking the surface water with dust-free paper.
(5) And (3) placing the sample obtained in the step (4) in air or a low-temperature environment for about 1 hour, and preparing the sample successfully after the gelatin in the graphene aerogel is solidified.
The graphene/gelatin sample is prepared by the steps, and the area size of the sample is 0.25cm 2 Testing the cycle performance of the glass substrate in water under 5N precompression, knotsThe result is shown in fig. 10. The sample had an adhesion strength of 61.4kPa after 1500 cycles of adhesion-desorption.
Example 5:
the preparation method of the underwater super-strong circulating adhesive material provided in the embodiment 5 comprises the following steps: preparing a carbon nano tube forest as a template material, wherein a monomer liquid is an aniline aqueous solution, and the method comprises the following detailed steps of:
(1) The water-assisted chemical vapor deposition method is adopted to grow the carbon nanotube forest as a template material. The preparation method of the carbon nanotube forest in the embodiment 2 is the same as that of the embodiment 1, and the density of the carbon nanotube forest can be prepared to be 22mg/cm 3 The height was 620. Mu.m.
(2) Preparing ammonium persulfate solution with the mass fraction of 10%, and placing the ammonium persulfate solution in a low-temperature environment to be cooled to 4 ℃ for standby.
(3) 2mL of deionized water was measured and placed in a petri dish, and 800. Mu.L of 50% phytic acid solution was added and mixed well. 200 mu L of aniline is continuously added, the mixed solution is magnetically stirred to be colorless and transparent, and the mixed solution is placed in a low-temperature environment and cooled to 4 ℃ for standby. The ratio of the added 50% phytic acid solution to the aniline can be adjusted between 4 and 5.
(4) Immersing the carbon nanotube forest prepared in the step (1) in the colorless transparent liquid prepared in the step (3), and placing the carbon nanotube forest in a low-temperature environment at 4 ℃ for about 2 hours.
(5) 1mL of the solution obtained in the step (2) is taken and added into a culture dish in the step (4), and chemical crosslinking reaction is carried out in a low-temperature environment at 4 ℃ for at least 8 hours.
(6) And (3) taking out the carbon nanotube array obtained in the step (6), and washing superfluous reaction products on the surface by using deionized water, so that the sample is successfully prepared.
The carbon nano tube/polyaniline sample is prepared by the steps, and the area size of the sample is 0.25cm 2 The cycle performance on a glass substrate in water under 5N pre-stress was tested and the results are shown in FIG. 11. The sample had an adhesion strength of 27kPa after 8000 cycles of adhesion-desorption.
Comparative example 1:
the present control example uses a carbon nanotube array and polydopamine solution to prepare a suitable compositionAnd (3) adhering the carbon nano tube dry glue under water. And (3) dripping the polydopamine solution around the carbon nanotube array with the height of 357 mu m, placing the polydopamine solution on a hot table for heating, and coating the polydopamine on the surface of the carbon nanotube array after the solution is evaporated, thereby obtaining the polydopamine modified carbon nanotube dry adhesive. The selected area is 0.25cm 2 The adhesive strength of the dry adhesive under 15N precompression is tested by a digital display tensile machine, and the adhesive strength is 306kPa. The cycle performance was tested and found to have an adhesion performance of 0 in the second test, indicating that the dry adhesive had excellent adhesion performance but no cycle performance.
The reason for the result is analyzed, the adhesive material obtained by the preparation method of the comparative example exists at the top end of the carbon nano tube array in a granular form, and the polydopamine does not undergo a crosslinking reaction. The carbon nanotube/polydopamine samples did not form a sealing structure, vertically oriented pore channels, and surface pore structures. Therefore, the material has no cyclic adhesion performance, is only suitable for being used as underwater disposable glue, and is not suitable for being used as an underwater cyclic adhesion material.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. An underwater super strong cyclic adhesion material, which is characterized in that: the structure of the underwater super-strong circulating adhesive material is as follows:
(1) The adhesion surface is the combination of the hole-shaped part and the plane part;
(2) The top surface and the periphery are of a sealing structure; the top surface is the surface opposite to the adhesion surface;
(3) The inside is a directional hole channel structure vertical to the adhesion surface;
the area of the hole-shaped part of the adhesion surface accounts for 20% -90% of the total area.
2. The underwater super-strong circulating adhesive material of claim 1, wherein: the pore radius of the pore-shaped part in the adhesion surface is 1-10 microns; the ratio of the height H of the directional hole channel vertical to the adhesive surface to the side length d of the adhesive surface is in the range of 0.001-10.
3. The underwater super-strong cyclic adhesion material of claim 1 or 2, wherein: the underwater superstrong cyclic adhesion material is a composite material of a three-dimensional structure material with vertical orientation and a high polymer material; wherein the three-dimensional structural material with vertical orientation comprises one or more of carbon nanotube forest, silicon nanowire forest, graphene with honeycomb structure and MXene aerogel; the polymer material comprises one or more of polyvinyl alcohol water, gelatin, polyaniline, polydimethylsiloxane and polyurethane acrylic ester.
4. The method for preparing the underwater super-strong cyclic adhesion material as claimed in claim 1, which is characterized in that: the method comprises the following steps:
(1) Preparing a three-dimensional structure material with vertical orientation, and taking the three-dimensional structure material as a template material;
(2) The polymeric liquid is infiltrated into the template material and the template material is sealed by physical and/or chemical action.
5. The method for preparing the underwater super-strong cyclic adhesion material according to claim 4, wherein the method comprises the following steps: the template material with the vertical orientation three-dimensional structure comprises one or more of a carbon nano tube forest, a silicon nano wire forest, graphene with a honeycomb structure and MXene aerogel, and the structural parameters of the template material can be regulated and controlled.
6. The method for preparing the underwater super-strong cyclic adhesion material according to claim 4 or 5, wherein the method comprises the following steps: the polymer liquid comprises one or more of polyvinyl alcohol aqueous solution, gelatin aqueous solution, aniline aqueous solution, polydimethylsiloxane and polyurethane acrylic ester.
7. The method for preparing the underwater super-strong cyclic adhesion material according to claim 4 or 5, wherein the method comprises the following steps: the viscosity of the polymer liquid ranges from 1cs to 3000cs, so that the polymer liquid can penetrate into the template material.
8. The method for preparing the underwater super-strong cyclic adhesion material according to claim 4 or 5, wherein the method comprises the following steps: the physical and/or chemical action includes curing, physical crosslinking, chemical crosslinking.
9. Use of an underwater super-strong cyclic adhesion material as claimed in claim 1, characterized in that: the adhesive material can be applied to underwater environment, air environment and solution environment;
the solution environment comprises electrolyte solution, ethanol and silicone oil; the underwater super-strong cyclic adhesion material can be applied to a substrate, wherein the substrate comprises one or more of glass, stainless steel, copper, aluminum and polytetrafluoroethylene.
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