CN115926348A - Underwater super-strong circulation adhesive material and preparation method and application thereof - Google Patents
Underwater super-strong circulation adhesive material and preparation method and application thereof Download PDFInfo
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Images
Abstract
The invention discloses an underwater super-strong circulation adhesive material and a preparation method and application thereof, wherein the underwater super-strong circulation adhesive material has the following structure: the adhesive surface is the combination of the hole-shaped part and the plane part; the top surface and the periphery are provided with sealing structures; the interior is a vertically oriented pore channel structure. The underwater super-strong circulation adhesive material can be applied to various liquid environments such as air, water, silicon oil and the like, and has excellent circulation adhesive performance on substrates such as glass, copper, polytetrafluoroethylene and the like. Therefore, the underwater super-strong circulation adhesive material 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 adhesion materials, and particularly relates to an underwater super-strong circulation adhesion material as well as a preparation method and application thereof.
Background
The underwater robot needs an adhesion 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, research on underwater adhesive materials is continuously advanced, and the underwater adhesive materials can be classified into two types, namely glue type adhesive materials and adhesive tape type adhesive materials according to the physical form of the adhesive materials. The glue-water type adhesive material is in a liquid form, and increases cohesion through a curing process to realize strong underwater adhesion. However, the adhesive material has the defects of long curing time, non-recyclability and the like, and is generally used as underwater permanent adhesive. The adhesive tape type adhesive material is in a solid form, has a simple process of adhesion and can be directly adhered to a substrate by pressing.
At present, the adhesive tape type adhesive material can be divided into hydrogel and a bionic micro-nano array. The hydrogel material realizes underwater adhesion through the action of hydrogen bonds or electrostatic force and the like, can realize stronger underwater adhesion, but has poor cycle performance (less than or equal to 50 times). For example, the Xuanfeng professor of the university of oceans in China and the doctor Petri Murto, university of Cambridge in England, synthesized a series of polymer gels that showed efficient and stable adhesion on the surface of different underwater objects with adhesion strengths as high as 840kPa, but which could achieve only 5 cycles of adhesion. The reason why the hydrogel material is poor in cycle properties is that the structure thereof is easily broken during adhesion-desorption. The bionic micro-nano array firstly removes water on an interface through a bionic micro-nano structure, and further realizes underwater adhesion through the actions of suction, capillary force or van der Waals force and the like. The bionic micro-nano array has good cycle performance, but the adhesion strength is low. For example, changshun Pang project group reported in Nature a study of an underwater adhesion material that mimics an octopus sucker array. The material can realize the underwater adhesion cycle performance of 10000 times, but the underwater adhesion strength is only 40kPa. The reason why the bionic micro-nano array can realize high cycle performance is that the structure of the bionic micro-nano array is not damaged in adhesion-desorption cycle, but the drainage efficiency is poor, and the preparation process of the material limits the breakthrough of the bionic micro-nano array on high adhesion performance.
For an underwater robot needing to operate for many times for a long time, the cycle performance of the hydrogel material and the adhesion performance of the bionic micro-nano array can not meet the use requirements of the underwater robot. In order to meet the operation requirement of an underwater robot, an underwater super-strong circulation adhesive material is needed, and super-strong is defined as that the number of circulations is more than 100. In recent years, underwater adhesive materials based on the suction effect have received much 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 ultrahigh cycle performance based on a suction effect, and the adhesion performance is improved through the structural design of the material, so that the underwater super-strong cycle adhesion material with high adhesion strength and high cycle performance is finally developed.
Disclosure of Invention
In response to the above-identified deficiencies in the art or needs for improvement, the present invention provides an underwater super-strong circulation adhesive material. The invention utilizes template material with vertical orientation three-dimensional structure and high molecular material to prepare underwater super-strong circulation adhesive material with vertical orientation hole channel and surface hole structure. The provided preparation method can realize accurate regulation and control of material adhesion performance, and successfully develop the underwater super-strong circulation adhesion material with high adhesion strength and high circulation performance. The technical problem that the high adhesion strength and the high cycle performance of an underwater adhesion material are difficult to combine is solved, and the application requirements in the fields of underwater robots and the like are met.
In order to achieve the above objects, according to one aspect of the present invention, there is provided an underwater super-strong circulation adhesive material, which has a structure including:
(1) The adhesive surface is the combination of the hole-shaped part and the plane part;
(2) The top surface and the periphery are provided with sealing structures;
(3) The interior is a vertically oriented pore channel structure.
The top surface refers to the surface opposite the adhesion surface.
Furthermore, in the structure of the underwater super-strong circulation adhesive material, the hole-shaped part and the plane part of the adhesive surface can respectively generate a suction effect under the action of pre-pressure, the plane part of the adhesive surface can generate a capillary force effect, and the combination of the hole-shaped part and the plane part can realize the underwater adhesive performance; the sealing structures on the top surface and the periphery are the precondition for generating the suction force. When the adhesion material is exerted with pulling force to enable the adhesion material to be gradually separated from the substrate, the suction force and the capillary force are damaged to realize desorption, and the vertical orientation hole channel structure provides good mechanical property to ensure that the structure of the material is not damaged in multiple adhesion-desorption processes, so that the super-strong circulation performance is realized.
Further, the proportion of the area of the hole-shaped part of the adhesion surface in the total area ranges from 20% to 90%.
Further, the preparation method for realizing the special structure of the underwater super-strong circulation 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 polymer liquid penetrates into the template material and seals the template material by physical and/or chemical action.
Further, in the preparation method of the underwater super-strong circulation adhesive material, the template material with the vertical orientation three-dimensional structure comprises a carbon nano tube forest, a silicon nano wire forest, graphene with a honeycomb structure or MXene aerogel 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 circulation adhesive material, the polymer liquid comprises polymer aqueous solutions such as polyvinyl alcohol aqueous solution, gelatin aqueous solution and the like, polydimethylsiloxane, polyurethane acrylate and the like.
Furthermore, the type of the high polymer in the high polymer liquid in the preparation method of the underwater super-strong circulation adhesive material is not limited to one, and two or more than two types of high polymers can be used simultaneously. The viscosity range of the high molecular liquid is 1cs-3000cs, so that the high molecular liquid can penetrate into the template material with certain popularity.
Further, the physical or/and chemical action in the preparation method of the underwater super-strong circulation adhesive material comprises solidification, a physical crosslinking method, a chemical crosslinking method and the like.
Further, the underwater circulation adhesion material can be applied to not only an underwater environment but also an air environment and other liquid environments. Other liquids include electrolyte solutions such as NaCl solution, silicone oil, and the like. The underwater circulation adhesion material can be applied to various kinds of substrates including glass, stainless steel, copper, aluminum, teflon, etc.
Compared with the prior art, the underwater super-strong circulation adhesive material provided by the invention mainly has the following beneficial effects:
(1) The invention realizes the development of the underwater super-strong circulation adhesive material by designing a special structure with the top surface and the periphery sealed, the bottom surface (namely the adhesive surface) provided with a porous structure and the inside provided with a vertically-oriented pore channel. The porous and planar structures of the adhesive side may drain away a portion of the water on the substrate when the material is immersed in water in contact with a target substrate and pre-stressed. After releasing the pre-pressure, the residual water on the substrate is sucked into the sample and locked. 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 porous structure of the adhesion surface, so that a suction effect is generated. Due to the presence of the three-phase medium, the planar structure of the adhesion surface generates a capillary force action. The combination of suction and capillary forces can achieve high adhesion performance. In addition, the good mechanical properties of the sample ensure that the structure of the sample is not damaged in the adhesion-desorption cycle, thereby achieving high cycle performance.
(2) According to the preparation method of the underwater super-strong circulation 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 precise regulation and control of the material performance can be realized, so that the preparation method is suitable for different application scenes. Specifically, the area ratio of the hole structure of the adhesion surface is an important parameter influencing the adhesion performance of the material, and the controllable adjustment of the underwater adhesion performance of the material can be realized by regulating the area ratio of the hole structure.
(3) The underwater super-strong circulation adhesive material simultaneously realizes high adhesive strength and high circulation performance. In particular, the adhesion strength of the developed material on the underwater glass substrate can reach 210kPa, and the adhesion performance can be kept stable in 30000 adhesion-desorption times. The adhesion strength and the cycle performance of the material under water are obviously superior to those of the underwater super-strong cycle adhesion material in other current researches. In addition, the underwater super-strong circulation adhesive material can be applied to the air and various liquid environments such as water, silicon oil and the like, and has excellent circulation adhesive performance on substrates such as glass, copper, polytetrafluoroethylene and the like. Therefore, the underwater super-strong circulation adhesive material 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 circulation adhesive material has simple preparation process and high efficiency, and is expected to be industrially produced and popularized and used on a large scale.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
fig. 1 is a schematic structural diagram of an underwater super-strong circulation adhesive material provided by the invention.
FIG. 2 is a schematic diagram of the preparation process of example 1.
FIG. 3 is a scanning electron micrograph of the adhesive material obtained in example 1.
FIG. 4 shows the adhesion behavior in water of the adhesive material obtained in example 1 with different structural parameters.
FIG. 5 shows the circulation behavior in water of the adhesive material obtained in example 1.
FIG. 6 adhesion performance of the adhesive 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, and silicone oil.
FIG. 8 shows the adhesion properties of the adhesion material obtained in example 2 in underwater circulation.
FIG. 9 shows the adhesion properties of the adhesion material obtained in example 3 in underwater circulation.
FIG. 10 shows the adhesion properties of the adhesion material obtained in example 4 in underwater circulation.
FIG. 11 shows the adhesion properties of the adhesion material obtained in example 5 in underwater circulation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Referring to fig. 1, the underwater super-strong circulation adhesive material provided by the present invention has a structure that (1) an adhesive surface (i.e., a bottom surface) is a combination of a hole-shaped portion and a plane portion; (2) the top surface and the periphery are sealed; (3) the interior is a vertically oriented pore channel structure. Wherein the hole-shaped part and the plane part of the adhesion surface can generate suction and capillary force to form strong adhesion under water; the tightness of the top surface and the surroundings is a prerequisite for the generation of suction. The internal vertically oriented pore channel structure provides good mechanical properties to achieve the underwater super-strong circulation performance of the material.
The preparation method for forming the structure comprises the following steps:
(1) And preparing a three-dimensional structure material with vertical orientation, and using the three-dimensional structure material as a template material. (2) The polymeric liquid is infiltrated into the template material and the template material is encapsulated by one or more of physical crosslinking, chemical crosslinking, and curing.
The structure of the underwater super-strong circulation adhesive material provided by the invention can change the parameters of the preparation process for adjustment, and finally the underwater adhesive material with high adhesion performance and high circulation performance 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 as the high polymer liquid. The preparation flow is shown in figure 2, and the detailed preparation steps are as follows:
(1) The carbon nano tube array is prepared as a template material by a water-assisted chemical vapor deposition method, and the method comprises the following specific steps: (1) plating an aluminum buffer layer and an iron catalyst layer on the surface of the single-side polished silicon wafer by a magnetron sputtering method. Wherein 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 sputtering 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) putting 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 gas in the growth process is 2000sccm, wherein the content proportion of ethylene is 20%, the content proportion of hydrogen is 5-20%, the content proportion of argon is 35-50%, the content proportion of argon carrying water vapor is 25%, the growth temperature is 780 ℃, and the growth time range 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 a water bath heating method. The heating temperature is 85-90 ℃, and the heating time is about 30 minutes. In order to facilitate the polyvinyl alcohol aqueous solution to penetrate into the carbon nanotube forest, the mass fraction of the polyvinyl alcohol aqueous solution can be 1%, 3%, 5%, 7% and the like.
(3) And (3) immersing the carbon nano tube forest obtained in the step (1) in the polyvinyl alcohol aqueous solution obtained in the step (2), heating the forest in a water bath at 70 ℃ for about 20 minutes, and observing that bubbles do not appear on the surface of the forest of the carbon nano tubes, thus finishing the water bath.
(4) And (4) taking the carbon nanotube forest in the step (3) out of the polyvinyl alcohol aqueous solution, washing the polyvinyl alcohol aqueous solution on the surface of the carbon nanotube forest by using deionized water, and sucking away the water on the surface by using dust-free paper.
(5) And (4) placing the carbon nano tube forest obtained in the step (4) in a freezing chamber at the temperature of-20 ℃, taking out the forest after 24 hours, unfreezing the forest to room temperature, and then placing the forest in the freezing chamber. And performing multiple freezing-thawing operations to physically crosslink polyvinyl alcohol in the carbon nanotube forest, and finally forming a vertical oriented pore channel and a surface pore structure under the combined action of the carbon nanotube forest and the polyvinyl alcohol.
The carbon nano tube forest/polyvinyl alcohol sample with the proportion of the area of the porous part on the adhesive surface to the total area being 0.2-0.9 can be prepared by the steps, and the area of the sample is 0.25cm 2 . A scanning electron micrograph of a sample in which the area ratio of the pore structure is 0.22 is shown in FIG. 3. Applying 5N pre-pressure on the samples to adhere to an underwater glass substrate, and testing the adhesive force of the samples by a digital display tensile machine. The samples having pore structure area ratios of 0.22, 0.35, 0.48, 0.67 and 0.88 were obtained with adhesive strengths of 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 (i.e. 48%) was subjected to a cyclic test on a glass substrate under a pre-pressure of 5N, and the result is shown in fig. 5, wherein the adhesion strength of the sample after 32000 adhesion-desorption cycles is 87.6kPa, which indicates that the sample has an ultra-strong cyclic adhesion capability. To verify the applicability of the samples on different substrates underwater, the samples were adhered to underwater glass, stainless steel, copper, aluminum and polytetrafluoroethylene substrates with a pre-stress of 15N and adhesion strengths of 210kPa, 200kPa, 175kPa, 190kPa, 160kPa, respectively, as shown in fig. 6, as measured by a digital tensiometer. In addition, to verify the applicability of the samples in different environments, the samples were adhered to a glass substrate in air, ethanol and silicone oil environments with a pre-pressure of 15N, respectively, and the adhesion strengths were 150kPa, 260kPa, 350kPa, respectively, as shown in fig. 7, by a digital tensile machine test.
Example 2:
the preparation method of the underwater super-strong circulation adhesive material provided by the embodiment 2 comprises the following steps: preparing a carbon nano tube forest as a template material, and selecting a polyvinyl alcohol-polydopamine mixed aqueous solution as a high-molecular liquid. The detailed preparation steps are as follows:
(1) Method for growing carbon nano tube by adopting water-assisted chemical vapor deposition methodForest, as template material. In this example 2, the method for preparing the carbon nanotube forest was the same as that in example 1, and the forest density of the prepared carbon nanotubes was 21mg/cm 3 And a height of 550 μm.
(2) And preparing a polydopamine suspension. 20mg of dopamine hydrochloride is weighed and placed in a reaction flask A, and 10mL of deionized water is added to be fully dissolved. 30mg of Tris (hydroxymethyl) aminomethane is weighed and placed in a reaction bottle B, and 10mL of deionized water is added for full dissolution, so as to prepare a Tris solution. The Tris solution was added dropwise to the a solution, and the pH value of the solution was measured with pH paper to prepare a mixed solution having pH = 8.5. Adding magnetons 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 autopolymerization. After 14 hours of reaction, the deposition of the polymeric dopamine particles was observed, and the preparation of the polymeric dopamine 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 a water bath heating method. The heating temperature is 85-90 ℃, and the heating time is about 30 minutes. The mass fraction of the prepared polyvinyl alcohol aqueous solution can be 3%.
(4) And (3) dispersing the polydopamine suspension obtained in the step (1) by using an ultrasonic pulverizer, wherein the dispersion time is about 30 min.
(5) And (4) 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 3% polyvinyl alcohol aqueous solution and 2ml of a 2mg/ml polydopamine suspension are mixed to obtain a polyvinyl alcohol-polydopamine mixed solution having a polyvinyl alcohol concentration of 2.5%.
(6) And (3) immersing the carbon nano tube forest obtained in the step (1) in the polyvinyl alcohol-polydopamine mixed solution obtained in the step (5), heating the forest in a water bath at 70 ℃ for about 20 minutes, and observing that bubbles do not emerge on the surface of the carbon nano tube forest any more, so that the water bath is completed.
(7) And (4) taking the carbon nanotube forest in the step (6) out of the polyvinyl alcohol-polydopamine mixed solution, washing the polyvinyl alcohol-polydopamine mixed solution on the surface of the carbon nanotube forest with deionized water, and sucking away the water on the surface by using dust-free paper.
(8) And (4) placing the carbon nanotube forest obtained in the step (7) in a freezing chamber, taking out the forest after 24 hours, thawing to room temperature, and then placing the forest in the freezing chamber. And (3) carrying out physical crosslinking on polyvinyl alcohol in the carbon nanotube forest through multiple freezing-thawing operations, and finally forming a vertical oriented pore channel and a surface pore structure under the combined action of the carbon nanotube forest, the polyvinyl alcohol and polydopamine.
The carbon nano tube forest/polyvinyl alcohol/polydopamine sample is prepared by the steps, and the area size of the sample is 0.25cm 2 The cycle performance of the glass substrate in water under a pre-pressure of 5N was tested, and the results are shown in fig. 8. The sample has an adhesion strength of 72.4kPa after 30000 times of adhesion-desorption cycles, which shows that the sample prepared in the example 2 also has super-strong cycle adhesion performance.
Example 3:
the preparation method of the underwater super-strong circulation adhesive material provided by the embodiment 3 comprises the following steps: preparing a carbon nano tube forest as a template material, and selecting gelatin aqueous solution as the high polymer liquid. The detailed steps are as follows:
(1) And (3) growing a carbon nano tube forest by adopting a water-assisted chemical vapor deposition method to serve as a template material. In this example 3, the method for preparing the carbon nanotube forest is the same as that in example 1, and the density of the prepared carbon nanotube forest is 25mg/cm 3 And a height of 650 μm.
(2) An aqueous gelatin solution was prepared. Weighing a proper amount of gelatin, placing the gelatin in deionized water, heating in a water bath at 60 ℃ to dissolve the gelatin, and then cooling the gelatin aqueous solution for later use, wherein the mass fraction of the gelatin in the prepared gelatin aqueous solution is 3%.
(3) And (3) immersing the carbon nano tube forest obtained in the step (1) in the gelatin aqueous solution obtained in the step (2), heating in water bath at 40 ℃ for about 15 minutes, and taking out the carbon nano tube forest from the gelatin aqueous solution after no bubbles emerge from the surface of the carbon nano tube forest.
(4) And (4) washing the gelatin water solution on the forest surface of the carbon nano tube obtained in the step (3) by using deionized water, and then absorbing water on the forest surface of the carbon nano tube by using dust-free paper.
(5) And (5) placing the sample obtained in the step (4) in the air or a low-temperature environment for about 1 hour, and curing the gelatin in the carbon nano tube forest to obtain a successful sample.
The carbon nano tube forest/gelatin sample is prepared by the steps, and the surface area of the sample adhesion surface is 0.25cm 2 The cycle performance of the glass substrate in water under a pre-pressure of 5N was tested, and the results are shown in fig. 9. The sample has an adhesion strength of 86.2kPa after 8000 times of adhesion-desorption cycles, which indicates that the sample prepared in the example 3 has super-strong cycle adhesion performance.
Example 4:
the preparation method of the underwater super-strong circulation adhesive material provided by the embodiment 4 comprises the following steps: preparing graphene aerogel with a honeycomb structure as a template material, and selecting gelatin aqueous solution as the high polymer liquid. The detailed steps are as follows:
(1) The preparation method of the graphene aerogel with the honeycomb structure comprises the following specific steps: (1) weighing a proper amount of graphene oxide powder, dissolving the graphene oxide powder in deionized water, and carrying out ultrasonic treatment for 5 hours to obtain a well-dispersed graphene oxide aqueous solution. (2) The aqueous graphene oxide solution was degassed in vacuo for 30 minutes. (3) And pouring the degassed graphene oxide aqueous solution into a pre-frozen mold, and then performing directional freezing for at least 24 hours. (4) Freeze-drying the sample obtained in step (3) for 72 hours at-70 deg.C under 0.1Pa. Finally preparing the graphene aerogel with the honeycomb structure.
(2) An aqueous gelatin solution was prepared. Weighing a proper amount of gelatin, placing the gelatin in deionized water, heating in a water bath at 60 ℃ to dissolve the gelatin, and then cooling the gelatin aqueous solution for later use, wherein the mass fraction range of the 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) And (4) washing the sample taken out in the step (3) by using deionized water, washing the gelatin aqueous solution on the surface of the sample, and sucking the water on the surface by using dust-free paper.
(5) And (5) placing the sample obtained in the step (4) in the air or a low-temperature environment for about 1 hour, and successfully preparing the sample after the gelatin in the graphene aerogel is solidified.
The graphene/gelatin sample is prepared by the steps, and the area of the sample is 0.25cm 2 The cycle performance of the glass substrate in water under a pre-pressure of 5N was tested, and the results are shown in fig. 10. The sample had an adhesive strength of 61.4kPa after 1500 adhesion-desorption cycles.
Example 5:
the preparation method of the underwater super-strong circulation adhesive material provided by the embodiment 5 comprises the following steps: preparing a carbon nano tube forest as a template material, selecting aniline aqueous solution as monomer liquid, and specifically comprising the following steps of:
(1) And (3) growing a carbon nano tube forest by adopting a water-assisted chemical vapor deposition method to serve as a template material. In this example 2, the method for preparing the forest of carbon nanotubes was the same as in example 1, and the forest density of carbon nanotubes was 22mg/cm 3 And a height of 620 μm.
(2) Preparing 10 mass percent ammonium persulfate solution, and placing the solution in a low-temperature environment to cool the solution to 4 ℃ for later use.
(3) 2mL of deionized water was weighed into a petri dish, and 800. Mu.L of 50% phytic acid solution was added and mixed well. Then, 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 into a low-temperature environment to be cooled to 4 ℃ for standby. The proportion of the added 50 percent phytic acid solution and the aniline can be adjusted between 4 and 5.
(4) And (3) immersing the carbon nano tube forest prepared in the step (1) in the colorless transparent liquid obtained in the step (3), and placing the forest in a low-temperature environment at 4 ℃ for about 2 hours.
(5) And (3) adding 1mL of the solution obtained in the step (2) into the culture dish in the step (4), and performing chemical crosslinking reaction at the low temperature of 4 ℃ for at least 8 hours.
(6) And (4) taking out the carbon nano tube array obtained in the step (6), and washing redundant 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 of the sample is 0.25cm 2 Testing the cycle performance of the glass substrate in water under the pre-pressure of 5N,the results are shown in FIG. 11. The sample had an adhesive strength of 27kPa after 8000 adhesion-desorption cycles.
Comparative example 1:
in this comparative example, a carbon nanotube dry glue suitable for underwater adhesion was prepared using a carbon nanotube array and a polydopamine solution. And dripping the polydopamine solution around the carbon nanotube array with the height of 357 mu m, placing the carbon nanotube array on a hot table, 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 glue. The selected area is 0.25cm 2 The adhesive strength of the dry adhesive under the pre-pressure of 15N under water is tested by a digital tensile machine, and the adhesive strength is 306kPa. The cycle performance of the adhesive is tested, and the adhesion performance is found to be 0 in the second test, which shows that the dry adhesive has excellent adhesion performance but no cycle performance.
Analyzing the reasons for the results, the adhesion material obtained by the preparation method of the comparative example was that polydopamine existed in the form of particles at the top of the carbon nanotube array, and no cross-linking reaction occurred in the polydopamine. The carbon nanotube/polydopamine samples did not form a sealing structure, vertically oriented pore channels, and surface pore structure. Therefore, the material does not have the circulating adhesion performance, is only suitable for being used as underwater disposable glue and is not suitable for being used as an underwater circulating adhesion material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An underwater super-strong circulation adhesive material is characterized in that: the underwater super-strong circulation adhesive material has the structure as follows:
(1) The adhesive surface is the combination of the hole-shaped part and the plane part;
(2) The top surface and the periphery are provided with sealing structures;
(3) The interior is a vertically oriented pore channel structure.
2. The underwater super-strong circulation adhesive material of claim 1, wherein: the proportion of the area of the hole-shaped part of the adhesive surface in the total area is 20-90%.
3. The underwater super-strong circulation adhesive material according to claim 1 or 2, wherein: the pore radius of the porous part in the adhesion surface is 1-10 microns, and the ratio of the height H of the vertically oriented pore channel to the side length d of the adhesion surface ranges from 0.001 to 10.
4. The underwater super-strong circulation adhesive material according to claim 1 or 2, wherein: the underwater super-strong circulation adhesive material is a composite material of a three-dimensional structure material with vertical orientation and a high polymer material; the three-dimensional structure material with vertical orientation comprises one or more of a carbon nano tube forest, a silicon nano wire forest, graphene with a honeycomb structure and MXene aerogel; the high molecular material comprises one or more of polyvinyl alcohol water, gelatin, polyaniline, polydimethylsiloxane and urethane acrylate.
5. The method for preparing the underwater super-strong circulation adhesive material of 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 polymer liquid penetrates into the template material and seals the template material by physical and/or chemical action.
6. The method for preparing the underwater super-strong circulation adhesive 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.
7. The method for preparing the underwater super-strong circulation adhesive 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 urethane acrylate.
8. The method for preparing the underwater super-strong circulation adhesive material according to claim 4 or 5, wherein: the viscosity range of the high molecular liquid is 1cs-3000cs, so that the high molecular liquid can penetrate into the template material.
9. The method for preparing the underwater super-strong circulation adhesive material according to claim 4 or 5, wherein: the physical and/or chemical action includes curing, physical crosslinking, chemical crosslinking.
10. The use of the underwater super-strong circulation adhesive material as claimed in claim 1, wherein: 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 circulation adhesive material can be applied to a substrate, and the substrate comprises one or more of glass, stainless steel, copper, aluminum and polytetrafluoroethylene.
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