Nano self-repairing coating robot and preparation method thereof

Abstract

The invention discloses a nano self-repairing coating robot and a preparation method thereof, and belongs to the technical field of ship carbon capture equipment. The nanometer self-repairing coating robot comprises a functional layer and a driving layer which are arranged in a combined mode, and the driving layer is arranged on the surface of the functional layer. The functional layer comprises a hollow core shell provided with a notch, and a repairing unit and a copolymer layer which are polymerized on the hollow core shell, and the repairing unit comprises an NH2-MXene repairing unit; the driving layer comprises a substrate material module, and a force sensing module, a positioning sensing module and a driving module which are integrated on the substrate material module. By constructing a multi-response intelligent repairing system, the surface damage of equipment can be repaired preliminarily in time, the NH2-MXene repairing unit is adopted as a repairing matrix, the damaged part can be repaired accurately, the mechanical performance of the coating is effectively guaranteed, the multi-field coupling driving technology is adopted, efficient repairing of corrosion damage is achieved, and the service life of the coating is prolonged. And long-acting and reliable protection is provided for ship carbon capture supergravity equipment.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ship carbon capture equipment, and more particularly relates to a nano self-repairing coating robot and a preparation method thereof. BACKGROUND

[0002] During the operation of the ship, the supergravity equipment is subjected to complex and harsh working conditions for a long time. The traditional self-repairing coating mainly relies on a passive diffusion mechanism to repair damage. When the ship encounters vibration (acceleration range of 0.5-1.5g), microcracks (width of 50-200nm) are easily generated on the surface of the equipment, but the traditional coating repair response time is long, usually more than 5 hours, the repair efficiency is low, and the microcracks may rapidly expand during the repair period, which seriously affects the integrity and service life of the equipment. Moreover, during the operation of the ship carbon capture supergravity equipment, the temperature fluctuation range is large, up to-40℃-120℃. Under the condition of severe temperature change, the adhesion of the traditional coating decreases by 50%, and the traditional repair agent easily fails under this temperature change condition, which cannot effectively maintain the protective performance of the coating, and the temperature change adaptability is poor.

[0003] The marine salt spray environment of the ship operation has high corrosiveness, and the Cl⁻ concentration is as high as 3.5%. Under the environment of high chloride ion corrosion, the impedance of the traditional coating decays by 30% per year, the marine environment tolerance is poor, and it is difficult to meet the protection life requirement of 10 years of the ship carbon capture equipment. With the passage of time, the protective performance of the coating gradually decreases, which greatly increases the corrosion risk of the equipment. SUMMARY

[0004] The application is aimed at the technical problems in the prior art, and provides a nano self-repairing coating robot and a preparation method thereof.

[0005] To solve the above technical problems, the nano self-repairing coating robot provided by the application comprises a functional layer and a driving layer which are combined, the functional layer is a base layer, and the driving layer is arranged on the surface of the functional layer. The functional layer comprises a hollow core-shell provided with a notch, a repair unit and a copolymer layer polymerized on the hollow core-shell, and the repair unit comprises an NH2-MXene repair unit. The driving layer comprises a base material module and a force sensing module, a positioning sensing module and a driving module which are integrated on the base material module.

[0006] Preferably, the hollow core-shell composed of Al2O3@SiO2 particles is repaired by the gap for the filling of the repair unit; the copolymer layer is a PLGA-b-PNIPAM block copolymer layer, the copolymer layer covers the gap of the hollow core-shell, and the hydrogen bond strength at the junction of the block polymer and SiO2 is adjusted by temperature response; and the Al2O3@SiO2 is taken as the shell, the PNIPAM block copolymer is taken as the cover, and the NH2-MXene repair unit is taken as the content, so as to prepare the microcapsule with the core-shell structure. The base material module comprises a high-purity borosilicate glass layer, the force sensing module comprises a flexible circuit board PI layer arranged on the upper portion of the high-purity borosilicate glass layer, the positioning sensing module comprises a carbon nanotube-graphene gel layer, and the driving module comprises a TiO2 / Pt heterojunction PS layer.

[0007] Preferably, the Al2O3@SiO2 hollow core-shell is synthesized by a sol-gel method, and the preparation comprises the following steps: 1g of Al2O3 nanoparticles with a particle size of 50nm is uniformly dispersed in 100 mL of an ethanol solvent, then 2g of tetraethyl orthosilicate and 0.1g of 25wt% ammonia water are added, and a SiO2 shell layer is formed on the surface of the Al2O3 nanoparticles by a sol-gel process at a temperature of 60℃ for 4 hours; After the reaction is completed, the product is calcined at 500℃ for 2 hours by using a mold to solidify the SiO2 shell layer, and Al2O3@SiO2 hollow core-shell particles with a particle size of 80nm and a shell thickness of 15nm are obtained.

[0008] Preferably, the prepared Al2O3@SiO2 hollow core-shell particles are loaded with a DOPA-TA composite coating, and the loading treatment steps are as follows: The prepared Al2O3@SiO2 hollow core-shell particles are dispersed in a Tris-HCl buffer solution with a pH value of 8.5, 100mg of dopamine with a concentration of 1mg / mL and 135mg of tannic acid with a concentration of 1.35mg / mL are sequentially added to the 100mL system, and the dopamine and tannic acid are self-assembled to form a uniform composite coating on the surface of the Al2O3@SiO2 particles by hydrogen bonding and electrostatic interaction under the condition of room temperature and stirring for 24 hours.

[0009] Preferably, the repair unit comprises a double-network hydrogel matrix and a MXene nanoplatelet reinforcing phase, the double-network hydrogel matrix takes a PAAm / PAA double-network hydrogel as a precursor, and the preparation of the double-network hydrogel matrix comprises the following steps: S1, synthesis of a first network hydrogel: The acrylamide monomer and N,N'-methylene bisacrylamide are dissolved in deionized water in a mass ratio of 3:2 to maintain a solid content of 15%, oxygen in the system is excluded, and then 0.1% of ammonium persulfate and 0.05% of tetramethyl ethylenediamine are added to the system, and the polymerization reaction is initiated; the reaction system is placed in a constant temperature water bath at 60°C, and the reaction is continued for 4 hours to prepare the PAAm network hydrogel; S2, synthesis of the second network hydrogel: The acrylamide monomer and 0.5 wt% of N,N'-methylene bisacrylamide are uniformly mixed, 1.5 M sodium hydroxide solution is added, the pH value of the solution is adjusted to 7.0, 0.3 wt% of ammonium persulfate is added to the reaction system under the condition of a temperature of 68~73°C to initiate free radical polymerization, and the reaction is continued for 6 hours to prepare the PAA network hydrogel; S3, formation of the interpenetrating network: The prepared PAA network hydrogel is soaked in an aqueous solution containing 10 wt% acrylamide monomer, 0.1 wt% N,N'-methylene bisacrylamide crosslinker, and 0.2 wt% ammonium persulfate initiator, and is swelled at 30°C for 24 hours to allow the hydrogel to fully absorb the monomer solution, and then the system is warmed to 68~73°C and reacted for 6 hours to initiate in-situ polymerization of the acrylamide inside the PAAm network to form the interpenetrating polymer network hydrogel.

[0010] Preferably, the preparation of the MXene nanoplatelet reinforcing phase comprises the following steps: S1, raw material pretreatment First, Ti3C2Tx MXene is prepared by HF etching, and then ultrasonic stripping treatment is performed to disperse the MXene platelets, and pure MXene platelets are collected by centrifugation; S2, surface grafting reaction The collected MXene platelets are uniformly dispersed in an ethanol solution containing 3-aminopropyltrimethoxysilane with a volume fraction of 5%, and the pH value of the solution is adjusted to 4.5, and the reaction is continued to graft amino functional groups on the surface of the MXene by amide reaction; The collected MXene platelets are uniformly dispersed in an ethanol solution containing 3-aminopropyltrimethoxysilane with a volume fraction of 5%, and 1~3 grams of 3-aminopropyltrimethoxysilane is added per gram of MXene, which is dissolved in an appropriate amount of 5 vol% ethanol solution, and 75 mL of solution is added per gram of MXene, and the pH value of the solution is adjusted to 4.5, and the reaction is continued to graft amino functional groups on the surface of the MXene by amide reaction; S3, post-treatment After the reaction is completed, the product is repeatedly washed with deionized water until it is neutral, and unreacted substances and impurities are removed. The modified NH2-MXene repair unit is obtained by using freeze-drying technology.

[0011] Preferably, the preparation of the copolymer layer comprises the following steps: D, L-lactide and N-isopropyl acrylamide are dissolved in toluene solvent at a molar ratio of 50:30 to form a solution with a total monomer concentration of 1.0 mol / L. Then, 0.05 wt % of stannous octoate is added as a catalyst, and the reaction is carried out at 110°C for 24 hours to synthesize the amphiphilic block copolymer through ring-opening polymerization.

[0012] Preferably, the core-shell interface polymerization is carried out by thiol-ene click reaction, comprising the following steps: A thiol-containing silane coupling agent is grafted on the surface of SiO2 through hydrosilylation to form an active interface with a decreasing density of thiol groups from the edge to the center. End-functionalized PLGA is prepared by reversible addition-fragmentation chain transfer polymerization 100 -b-PNIPAM 50 The block copolymer has PLG segments as hydrophobic anchoring segments on the surface of SiO2, and PNIPAM segments as temperature-sensitive response segments. The grafting density is higher in the edge region than in the center region, forming a gradient grafting network with edge enrichment and center sparseness.

[0013] Preferably, the force sensing module preparation comprises the following steps: A resistance pattern with a width of 5 μm and a length of 50 μm is photoetched on a high-purity borosilicate glass substrate using electron beam lithography technology. Then, the excess glass material is removed by wet etching process to form the resistance structure. A layer of nickel-chromium alloy with a thickness of 200 nm is deposited on the surface of the resistance as a sensitive material by magnetron sputtering technology, and then high-temperature annealing treatment is carried out. The positioning sensing module preparation comprises the following steps: A carbon nanotube-graphene composite structure is grown on a silicon wafer substrate with a mass ratio of 1:3~1:5. After ultrasonic dispersion to a solution of 2~5 mg / mL, 0.5~1 wt% chitosan is cross-linked to prepare a gas gel with a porous structure. Then, the surface of the gas gel is treated with amino groups, and the gas gel is immersed in a 1~3 wt% 3-aminopropyltrimethoxysilane ethanol solution at a mass ratio of 1:100~1:200. CdSe quantum dots are synthesized and loaded on the surface of the amino-functionalized carbon nanotube-graphene aerogel by electrostatic adsorption. Then, a layer of Ti3C2Tx MXene is deposited on the surface of the quantum dot-loaded aerogel to construct a fluorescence resonance energy transfer system.

[0014] Preferably, the preparation method of the driving module comprises the following steps: S1, polystyrene microspheres are used as templates, and double-metal layer deposition is carried out on the surface of the polystyrene microspheres by using atomic layer deposition technology, the polystyrene microspheres are placed in an atomic layer deposition reaction cavity, TiCl4 and H2O are introduced as precursors, and atomic layer deposition reaction is carried out at a temperature of 150 DEG C; S1, polystyrene microspheres are used as templates, and double-metal layer deposition is carried out on the surface of the polystyrene microspheres by using atomic layer deposition technology, the polystyrene microspheres are placed in an atomic layer deposition reaction cavity, TiCl4 and H2O are introduced as precursors, and atomic layer deposition reaction is carried out at a temperature of 150 DEG C; S2, the precursors are switched to Pt(acac)2 and O2, atomic layer deposition reaction is continued at a temperature of 250 DEG C, and a TiO2 / Pt heterostructure is formed; S3, the polystyrene microsphere template is removed by O2 plasma etching, and a Janus nanoparticle with a TiO2 / Pt heterostructure is obtained.

[0015] Compared with the prior art, the present application has the following beneficial effects: The present application can timely repair the surface damage of the equipment by constructing a multi-response intelligent repair system through the functional layer and the driving layer, and the nanometer self-repairing coating robot can accurately repair the damaged parts by using the NH2-MXene repair unit obtained by MXene modification as the repair matrix, thereby effectively guaranteeing the mechanical properties of the coating. In addition, the driving layer of the external core-shell has a temperature response repair agent release mechanism and a light-heat / chemical multi-driving mode, which can realize efficient repair of corrosion damage through coordinated action, thereby providing long-term and reliable protection for the ship carbon capture supergravity equipment and solving the problems of low repair efficiency and poor environmental adaptability of the traditional coating under complex working conditions of the ship. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0017] Figure 1 It is an assembly structure diagram of the nanorobot embodiment of the present application. Figure 2 It is a structure diagram of the driving layer embodiment of the present application.

[0018] Explanation of symbols in the figure: 1, hollow core-shell; 2, repair unit; 3, copolymer layer; 4, base material module; 5, force sensing module; 6, positioning sensing module; 7, driving module. DETAILED DESCRIPTION

[0019] In order to make the technical problems, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0020] EMBODIMENT Please refer to Figure 1 , Figure 2 The embodiment of the present application provides a kind of nanometer self-repairing coating robot and preparation method thereof, nanometer self-repairing coating robot includes the functional layer and driving layer combinedly arranged, functional layer is base layer, driving layer is arranged on the surface of functional layer; Functional layer includes hollow core-shell 1 with notch and repair unit 2, copolymer layer 3 polymerized on hollow core-shell 1, repair unit 2 includes NH2-MXene repair unit; Driving layer includes base material module 4 and integratedly arranged force sensing module 5, positioning sensing module 6 and driving module 7 on base material module 4.

[0021] The present application constructs multi-response intelligent repair system through functional layer and driving layer, can preliminarily repair the surface damage of equipment in time, nanometer self-repairing coating robot uses NH2-MXene repair unit obtained by MXene modification treatment as repair matrix, can accurately repair damage site, effectively guarantees the mechanical performance of coating;And adopt multi-field coupling driving technology, the modules of driving layer located in external core-shell have temperature response repair agent release mechanism and photo-thermal / chemical multi-driving mode, cooperate action to realize efficient repair to corrosion damage, provide long-acting, reliable protection for ship carbon capture supergravity equipment, solve the problem of low repair efficiency and poor environmental adaptability of traditional coating under complex working conditions of ship.

[0022] In the embodiment, hollow core-shell 1 is composed of gel matrix of Al2O3@SiO2 particles, and the notch is set to fill the repair unit;Copolymer layer 3 is PLGA-b-PNIPAM block copolymer layer, copolymer layer 3 covers the notch of hollow core-shell 1, and the hydrogen bond strength at the interface of block polymer and SiO2 is adjusted by temperature response;With Al2O3@SiO2 as shell, PNIPAM block copolymer as cover, NH2-MXene repair unit as content, a core-shell structure microcapsule is prepared.

[0023] Specifically, the nano self-repairing coating robot adopts temperature-responsive microcapsules (PLGA-b-PNIPAM), which have unique response characteristics. When the temperature is higher than 40℃, the temperature-responsive microcapsules can rapidly release the repairing agent within 5 minutes, so that the surface damage of the equipment can be preliminarily repaired in time.

[0024] In the embodiment, Al2O3@SiO2 hollow core-shell particles are used as the base material of the temperature-responsive microcapsules. The hollow core-shell 1 adopts particles with a particle size of 80 nm and a shell thickness of 15 nm. The end of the hollow core-shell 1 has a notch for filling the NH2-MXene repairing unit. The hydrogen bond strength between the temperature-adjusted block polymer and SiO2 at the joint is adjusted to realize the controlled release of the core-shell content.

[0025] The copolymer layer 3 covers the notch of the Al2O3@SiO2 hollow core-shell. The opening and closing of the polymer edge are realized through temperature response, so as to adjust the controlled release of the NH2-MXene repairing unit. Then, the NH2-MXene repairing unit as the equipment coating repairing module can accurately repair the damaged part by using the repairing technology, restore the integrity and performance of the coating, and effectively protect the mechanical performance of the coating.

[0026] As shown in Figure 1 , Figure 2 In the embodiment, the base material module 4 includes a high-purity borosilicate glass layer, the force sensing module 5 includes a flexible circuit board PI layer arranged on the upper part of the high-purity borosilicate glass layer, the positioning sensing module 6 includes a carbon nanotube-graphene gel layer, and the driving module 7 includes a TiO2 / Pt heterojunction PS layer.

[0027] Specifically, the high-purity borosilicate glass layer is located on the surface of the Al2O3@SiO2 hollow core-shell base material and serves as the base material of the sensing module. The carbon nanotube-graphene gel layer is used as a quantum dot-based fluorescent positioning sensor. The TiO2 / Pt heterojunction PS layer is located on the upper part of the high-purity borosilicate glass layer and serves as a photo / chemical driving module.

[0028] When microcracks appear on the surface of the equipment, the changes in stress and strain around the cracks will cause changes in the distance and interaction between the quantum dots and the microcapsules, thereby causing changes in the fluorescence signal. Through accurate detection and analysis of the fluorescence signal, the position and size of the microcracks can be accurately determined, which provides key information for the timely and accurate repair of the nano robot. The embodiment of the present application combines photo-thermal driving and chemical driving to form a powerful multi-field coupling driving system.

[0029] In the embodiment, the Al2O3@SiO2 hollow core-shell is synthesized by a sol-gel method. The preparation method includes the following steps: Al2O3 nanoparticles with a particle size of 50 nm were uniformly dispersed in an ethanol solvent, then tetraethyl orthosilicate (TEOS) and ammonia were added, and the reaction was carried out at a temperature of 60°C for 4 hours to form a SiO2 shell layer on the surface of the Al2O3 nanoparticles through a sol-gel process; Al2O3 nanoparticles with a particle size of 50 nm (1 g) were uniformly dispersed in 100 mL of an ethanol solvent and ultrasonically treated for 30 minutes until the system was uniformly mixed; Then 2 g of tetraethyl orthosilicate (TEOS, with a mass ratio of 2:1 to Al2O3) was added and stirred for 30 minutes to mix uniformly; then 0.1 g of 25wt% ammonia water (about 12.5% of the molar mass of TEOS) was added dropwise to adjust the pH of the system to 8-10, and the reaction was carried out at a constant temperature of 60°C for 4 hours to form a SiO2 shell layer with a thickness of about 10-20 nm on the surface of the Al2O3 nanoparticles through a sol-gel process; After the reaction was completed, the product was calcined at 500°C for 2 hours using a specific mold to remove organic impurities and further solidify the SiO2 shell layer, and finally Al2O3@SiO2 hollow core-shell particles with a particle size of 80 nm and a shell thickness of 15 nm were obtained.

[0030] In this proportioning system, ethanol acts as a dispersion medium to ensure uniform distribution of Al2O3 particles, ammonia catalyzes the hydrolysis and condensation of TEOS, and the shell thickness is controlled by controlling the amount of silicon source, and finally Al2O3@SiO2 nanoparticles with uniform core-shell structure are obtained.

[0031] The preparation process used in this example can accurately control the particle size and shell thickness of the core-shell particles, ensuring good dispersibility and stability in the coating.

[0032] Further, the performance of the prepared core-shell was tested, and TEM observation showed that the core-shell interface was clear and had no obvious defects, indicating that the shell layer was tightly combined with the core; through XRD spectrum analysis, the SiO2 shell layer showed amorphous structure, which was beneficial to the subsequent loading and uniform distribution of DOPA-TA composite coating; the specific surface area was determined by BET method, and the Al2O3 core was 65 m² / g, and the core-shell particle was 32 m² / g, the change of specific surface area reflected the formation of core-shell structure and the influence of shell layer on the surface properties of particles.

[0033] Further, the prepared hollow core-shell particles were loaded with DOPA-TA composite coating, and the loading treatment steps were as follows: The prepared Al2O3@SiO2 hollow core-shell particles were dispersed in a Tris-HCl buffer solution with a pH value of 8.5, and 100 mg, 1 mg / mL of dopamine (DOPA) and 135 mg, 1.35 mg / mL of tannic acid (TA) were sequentially added to the 100 mL system, at this time, the mass ratio of Al2O3@SiO2 particles, dopamine and tannic acid was 1:1:1.35 (20:20:27).

[0034] Under the condition of room temperature, continuous stirring for 24 hours, dopamine and tannic acid self-assembled on the surface of Al2O3@SiO2 particles to form a uniform composite coating through hydrogen bonding and electrostatic interaction.

[0035] The self-assembly process in this embodiment is carried out under mild conditions, which can effectively avoid the damage to the structure of the core-shell particles, while ensuring the uniformity and stability of the composite coating.

[0036] Meanwhile, the core-shell repair particles have the following advantages: High loading capacity: through UV-Vis determination, the TA loading capacity reaches 0.8 mg / m 2 , and the DOPA loading capacity is 0.6 mg / m 2 , which realizes efficient loading of the composite coating on the surface of the core-shell particles, and appropriate loading capacity can fully exert the corrosion inhibition performance of DOPA and TA, while ensuring the dispersion of the core-shell particles in the coating; Excellent corrosion inhibition performance: through polarization curve test, in 3.5% NaCl solution, the coating corrosion current density of the core-shell repair particles is reduced from 1.2 μA / cm 2 to 0.2 μA / cm 2 , which indicates that it has good corrosion inhibition effect; the DOPA-TA composite coating can form a dense protective film on the surface of the coating, effectively inhibit the corrosion reaction of the metal, prolong the service life of the coating, and improve the protection performance of the ship carbon capture supergravity equipment.

[0037] In this embodiment, the NH2-MXene repair unit of the nanorobot includes a double network hydrogel matrix and a MXene nanosheet reinforcing phase, both of which are prepared by modification treatment to obtain the NH2-MXene repair unit as the matrix for equipment damage repair. The double network hydrogel matrix in the repair unit uses PAAm / PAA double network hydrogel as the precursor, and the MXene nanosheet as the reinforcing phase.

[0038] Specifically, the preparation of the repair unit includes the following steps: 1) First, the repair unit precursor is prepared, which is PAAm / PAA double network hydrogel, and a new step-by-step polymerization process is used to construct an interpenetrating network.

[0039] The preparation of the double-network hydrogel matrix comprises the following steps: S1, synthesis of the first network hydrogel (PAAm): The acrylamide (AM) monomer with a purity of 99% and N,N'-methylene bisacrylamide (BIS, crosslinking agent) are fully dissolved in deionized water at a mass ratio of 3:2, and the solid content is maintained at 15%. Nitrogen is introduced for 30 minutes to completely remove oxygen in the system. Then, 0.1% of ammonium persulfate (APS) and 0.05% of tetramethyl ethylenediamine (TEMED) are added to the system, accounting for 0.1% of the mass of the system, to initiate the polymerization reaction. The reaction system is placed in a constant temperature water bath at 60°C, and the reaction is continued for 4 hours, thereby forming a polyacrylamide (PAAm) network with physical crosslinking points. This network structure lays the foundation for the introduction of the PAA network, and the physical crosslinking points give the hydrogel certain initial flexibility and preliminary structural stability.

[0040] S2, synthesis of the second network hydrogel (PAA): The 99% pure acrylic acid (AA) monomer and 0.5 wt% mass fraction of N,N'-methylene bisacrylamide (BIS) are uniformly mixed to form a pre-polymerization solution. Then, 1.5 M sodium hydroxide solution is slowly added to adjust the pH value of the solution to 7.0, and the neutralization degree is about 60 mol%.

[0041] Under the condition of a water bath at 68~73°C (preferably 70°C), 0.3 wt% of ammonium persulfate (APS) is added to the reaction system to initiate free radical polymerization, and the reaction is continuously stirred for 6 hours to prepare a polyacrylic acid (PAA) network hydrogel by free radical polymerization.

[0042] The chemical crosslinking structure of the PAA network gives the hydrogel stronger mechanical properties and stability, and the PAAm network interweaves with the PAA network to form a unique interpenetrating network structure.

[0043] S3, formation of the interpenetrating network: The prepared PAAm network hydrogel is soaked in an aqueous solution containing 10 wt% acrylic acid monomer, 0.1 wt% N,N'-methylene bisacrylamide crosslinking agent, and 0.2 wt% ammonium persulfate initiator. The swelling-polymerization process is used to swell the hydrogel in a constant temperature shaking bed at 30°C for 24 hours, so that the hydrogel can fully absorb the monomer solution, and the swelling ratio is about 5~8 times.

[0044] Subsequently, the system is heated to 68~73°C for 6 hours to initiate in-situ polymerization of the acrylic acid monomer inside the PAAm network hydrogel, forming an interpenetrating polymer network hydrogel. After the reaction is completed, the hydrogel is washed repeatedly with deionized water for 3 times, each time for 12 hours, to remove the unreacted monomers.

[0045] Further, by precisely regulating the crosslinking density to 2.5 x 10⁻ 4 mol / cm³, the overall performance of the hydrogel is optimized, making it have both high elasticity and anti-swelling.

[0046] Further, the PAAm / PAA double network hydrogel is used as the precursor of the repair unit, and the performance of the precursor material of the repair unit is tested and verified.

[0047] Mechanical properties: According to ASTM D638 standard, it has excellent mechanical properties, the tensile strength of the hydrogel can reach 1.5 MPa, and the elongation at break can reach 550%, and the storage modulus is 350 kPa by dynamic mechanical analysis. Compared with traditional single network hydrogel, its tensile strength and elongation at break are significantly improved, which can better adapt to the complex stress environment during ship operation, effectively resist deformation and damage caused by vibration, impact, etc., and provide good flexibility and anti-deformation ability for nanorobots.

[0048] Anti-swelling: In the 3.5% NaCl solution simulating the marine environment, the equilibrium swelling degree of the hydrogel is ≤200%, which is significantly better than the 350% of the traditional single network hydrogel. This feature ensures that the hydrogel will not be damaged and its performance will not decrease due to excessive swelling in the marine salt spray environment, maintaining the integrity and protective performance of the coating.

[0049] FTIR characterization: FTIR analysis can clearly observe the amide I band characteristic peak of PAAm at 1660 cm -1 , and the carboxylic acid group characteristic peak of PAA at 1710 cm -1 , thereby confirming the successful synthesis of the two polymer networks. Through SEM observation, the bicontinuous network structure can be directly observed, with a pore size distribution of 50-200 nm. This microstructure provides an ideal space for the uniform dispersion and effective reinforcement of MXene nanosheets.

[0050] 2) A new amino-modification process is used to modify MXene to obtain NH2-MXene repair unit.

[0051] The preparation of MXene nanosheet reinforcing phase includes the following steps: S1, raw material pretreatment First, Ti3C2Tx MXene is prepared by HF etching, and then ultrasonic stripping treatment is performed to fully disperse the MXene sheet layer. Pure MXene sheet layer is collected by centrifugation operation; centrifugation operation is set to 8000 rpm for 30 minutes to provide high-quality raw materials for subsequent surface grafting reaction.

[0052] Specifically, on the basis of the original HF etching method for preparing Ti3C2Tx MXene, in order to reduce the safety risk and operation difficulty caused by the strong corrosiveness of HF, an improved scheme is proposed, in which a mixed solution of fluorinated salt (NaF or KF) and hydrochloric acid (HCl) is used as an etchant instead of HF solution, and the post-processing process is optimized. The specific steps are as follows: 1) Etchant preparation Mix NaF or KF with concentrated hydrochloric acid to prepare the etching solution.

[0053] Generally, the mass ratio of NaF or KF to concentrated hydrochloric acid is 1:2~1:3, for example, take 5g NaF, slowly add 10~15mL concentrated hydrochloric acid, and stir uniformly. This mixed solution can achieve etching of Ti3AlC2 by generating HF (NaF+HCl→HF+NaCl), while reducing the free concentration of HF and reducing the safety hazard.

[0054] 2) Etching reaction Take Ti3AlC2 powder as the precursor, and mix it with the above etching solution in a ratio of 1g Ti3AlC2 to 8~12mL etching solution.

[0055] For example, add 2g Ti3AlC2 powder to 20mL etching solution, and stir at a speed of 200~300r / min at room temperature for 50~65 hours. During the reaction, the HF in the mixed solution gradually etches the Al atomic layer in Ti3AlC2 to generate Ti3C2Tx MXene.

[0056] 3) Simplify centrifugation and washing After the reaction is completed, transfer the mixed solution to a centrifuge tube and use a stepwise centrifugation method.

[0057] First, centrifuge at a speed of 2000~3000r / min for 5~8 minutes to remove larger particulate impurities and retain the supernatant. Then, centrifuge the supernatant at a speed of 4000~5000r / min for 10~15 minutes to obtain MXene precipitate. Subsequently, directly add an ethanol-water mixed solution (volume ratio of ethanol to water is 1:3~1:5) to the centrifuge tube containing the precipitate for washing. The ethanol reduces the surface tension of MXene, reduces agglomeration, and effectively washes away residual etchant and byproducts. Repeat the washing 3~4 times, and centrifuge at a speed of 4000~5000r / min for 10~15 minutes after each washing to discard the supernatant.

[0058] 4) Ultrasonic exfoliation and collection The washed precipitate is dispersed in an isopropyl alcohol-water mixed solution (volume ratio of isopropyl alcohol to water is 1:2 to 1:3), the ultrasonic power is set to 80 to 150 W, and the ultrasonic time is extended to 4 to 10 hours to promote the full exfoliation of MXene layers.

[0059] After ultrasonic treatment, centrifugation is performed at a speed of 3000 to 4000 r / min for 15 to 20 minutes, and the upper layer of the dispersion liquid rich in MXene layers is collected, thereby obtaining pure MXene layers.

[0060] S2, surface grafting reaction The collected MXene layers are uniformly dispersed in an ethanol solution containing 3-aminopropyltrimethoxysilane (APTMS) with a volume fraction of 5%, 1 to 3 grams of 3-aminopropyltrimethoxysilane is added per gram of MXene, and the 3-aminopropyltrimethoxysilane is dissolved in an appropriate amount of 5vol% ethanol solution, 75 mL of solution per gram of MXene. The pH value of the solution is adjusted to 4.5 using a dilute hydrochloric acid solution, and the reaction is continuously stirred at room temperature for 8 to 12 hours to graft amino functional groups on the surface of MXene through an amidation reaction.

[0061] Under this ratio, 3-aminopropyltrimethoxysilane can fully react with the active groups on the surface of MXene, avoiding agglomeration caused by excessive 3-aminopropyltrimethoxysilane, while ensuring effective grafting of amino functional groups, thereby realizing surface modification of MXene. The reaction conditions are mild and controllable, which can effectively ensure the efficiency and stability of the grafting reaction.

[0062] S3, post-treatment process After the reaction is completed, the product is repeatedly washed with deionized water until it is neutral, and then the unreacted substances and impurities are removed. Then, a freeze-drying technique is used to obtain amino-functionalized MXene (NH2-MXene), and the modified NH2-MXene repair unit is obtained. The freeze-drying process can maximize the retention of the structure and properties of MXene, avoiding agglomeration and structural damage during the drying process.

[0063] Further, in this embodiment, MXene nanosheets are used as reinforcing phases to greatly improve the performance of the coating, with a strain sensitivity GF of 1800. In a 1500h salt spray environment, the impedance of the coating can still be maintained at 10 8 Ω·cm 2 , significantly enhancing the corrosion resistance of the coating.

[0064] The interface enhancement principle of the NH2-MXene repair unit is tested and verified.

[0065] High grafting density: XPS analysis revealed a nitrogen content of 2.3%, and the calculated grafting density reached 1.2 mmol / m². This high grafting density allows for the formation of more chemical bonding sites between MXene and the hydrogel matrix, effectively enhancing the interfacial bonding between the two.

[0066] High dispersibility: Adding 0.5% NH2-MXene to the hydrogel precursor solution and using ultrasonic dispersion technology (200W power, 30 minutes) allows NH2-MXene to form a stable suspension in the solution, achieving uniform dispersion in the hydrogel matrix. Uniformly dispersed NH2-MXene can fully exert its reinforcing effect, avoiding performance degradation caused by aggregation.

[0067] High composite material performance: Tests showed that compared with PAAm / PAA hydrogel without MXene, the tensile strength of the composite material with added NH2-MXene increased to 1.5 MPa (pure PAAm / PAA is 1.2 MPa), and the fracture energy increased by 40% (obtained by J-integral test). At the same time, the thermal stability was also significantly improved. TGA test showed that the initial decomposition temperature increased from 280℃ to 320℃, indicating that the introduction of NH2-MXene not only enhanced the mechanical properties of the hydrogel, but also improved its stability in high-temperature environments, making it more suitable for the complex working conditions of ship carbon capture hypergravity equipment.

[0068] In this embodiment, as Figure 1 As shown, NH2-MXene repair units are encapsulated using a PLGA-b-PNIPAM block copolymer layer. The preparation of the PLGA-b-PNIPAM block copolymer includes the following steps: D,L-lactide (PLGA) and N-isopropylacrylamide (PNIPAM) were dissolved in toluene at a molar ratio of 50:30 to form a solution with a total monomer concentration of 1.0 mol / L; for example, 5.806 g of D,L-lactide (0.05 mol) and 3.425 g of N-isopropylacrylamide (0.03 mol) were weighed and dissolved in 80 mL of toluene.

[0069] Then, 0.05 wt% of stannous octoate (Sn(Oct)2) was added as a catalyst. Under nitrogen protection, the reaction was carried out in an oil bath at 110°C with continuous stirring for 24 hours to synthesize an amphiphilic block copolymer via ring-opening polymerization.

[0070] After the reaction was completed, the product solution was cooled to room temperature and slowly added dropwise to 10 times its volume of ice-cold diethyl ether to precipitate the product. After filtration, the product was vacuum dried to constant weight to obtain a white powdered copolymer.

[0071] Further, by precisely controlling the raw material ratio, catalyst dosage and reaction temperature, the copolymer chain length and structure are precisely controlled. The synthesized product is purified by precipitation method using methanol / dichloromethane (volume ratio 3:1) as the precipitator to remove unreacted monomers and impurities.

[0072] Temperature response of the block copolymer: when the environmental temperature exceeds 40℃, the PNIPAM segment shrinks, causing the microcapsule to break, and the release rate constant k of the repair agent reaches 0.25min -1 The temperature response mechanism can release the repair agent in time when the temperature rises due to friction, heat generation and other reasons during equipment operation, meeting the repair needs under different working conditions.

[0073] In this embodiment, the reversible controlled release of the repair unit is realized under the temperature response of the block copolymer. By constructing a double-response grafting method, the grafting density gradient is constructed under the temperature gradient field, and the reversible interface reconstruction mechanism of the synergistic effect of disulfide bond and hydrogen bond is involved. The specific method is as follows: A new coupling agent 3,3'-dithiobispropyltrimethoxysilane (DTDPMS) is synthesized by introducing a reversible covalent bond unit, disulfide bond (-S-S-), into the traditional silane coupling agent. The coupling agent forms a dynamic covalent bond that can be broken and recombined on the surface of SiO2, and the PNIPAM segment forms a hydrogen bond network with the hydroxyl groups on the surface of SiO2.

[0074] When the temperature is higher than 40℃, the thermal cleavage (breakage energy 40 kJ / mol) of the disulfide bond and the dissociation of the hydrogen bond synergistically accelerate the shrinkage of the PNIPAM segment, and the opening of the shell edge allows the free diffusion of the repair unit NH2-MXene; when the temperature falls to 32℃, the disulfide bond is reformed under oxidation conditions, and the hydrogen bond network is restored to close the shell edge, realizing the reversible reconstruction of the grafting interface.

[0075] The temperature-sensitive behavior of the PNIPAM segment follows a "swelling-shrinking" second-order phase transition process: when the environmental temperature is lower than 32℃, the PNIPAM segment forms hydrogen bonds with water molecules and exists in a relaxed random coil conformation, at this time the interfacial tension (γ1=25 mN / m) of the edge region grafting chain is outward, which promotes the edge to be in an "open" state, allowing the free diffusion of the repair unit NH2-MXene; when the temperature rises above 40℃, the hydrophobic interaction between the isopropyl groups dominates, and the chain segment shrinks into a compact spherical conformation, and the interfacial tension drops to γ2=8 mN / m, under the hydrophobic tension of the PLGA anchoring segment, the edge bends inward and closes, and the hydrogen bond network restores to close the shell edge.

[0076] In this embodiment, the core-shell grafting is carried out by "thiol-ene click reaction", which specifically includes the following steps: Firstly, the silane coupling agent (3-mercaptopropyltrimethoxysilane, MPTMS) containing mercapto group was grafted on the surface of SiO2 by hydrosilylation reaction to form an active interface with the density of mercapto group decreasing from the edge to the center; meanwhile, the PLGA with double bond functionalization at the end was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization 100 -b-PNIPAM 50 The block copolymer, in which the PLGA segment (polymerization degree 100) serves as the hydrophobic anchoring segment on the surface of SiO2, and the PNIPAM segment (polymerization degree 50) serves as the temperature-sensitive response segment, has a grafting density (1.2 chains / nm 2 ) at the edge region significantly higher than that (0.3 chains / nm 2 ) at the center region, thereby forming a gradient grafting network with "edge enrichment-center sparseness", which is beneficial to the release of the repair unit at the center region.

[0077] Reversible controlled release of NH2-MXene in core-shell particles: The core-shell structure microcapsule is prepared with Al2O3@SiO2 as the shell, the PNIPAM block copolymer as the cover, and the NH2-MXene repair unit as the content. When the temperature is higher than 40℃, the edge opening state allows the free diffusion of NH2-MXene; when the temperature drops to 32℃, the edge closes to form a dense layer with a pore size <5nm, and the release of the repair unit stops.

[0078] In this embodiment, after the functional layer of the nanorobot is prepared, the driving layer assembly is started, and the functional layer surface is provided with a six-dimensional force tactile array sensor composed of six positioning and driving integrated units (a~f in Figure 1 The sensitive resistance structure is prepared on a high-purity borosilicate glass (Schott Group D263T glass) substrate by photolithography and etching processes using micro-electro-mechanical system (MEMS) processing technology.

[0079] Specifically, the force sensing module preparation includes the following steps: S1, glass micro-fusion strain gauge sensor preparation: First, the electron beam lithography technology is used to lithograph a resistance pattern with a width of 5μm and a length of 50μm on a high-purity borosilicate glass substrate, and then a wet etching process is used to remove the excess glass material to form an accurate resistance structure; Then, a layer of nickel-chromium alloy (NiCr) with a thickness of 200nm is deposited on the surface of the resistance as a sensitive material by magnetron sputtering technology, and finally high-temperature annealing treatment (400℃, 2 hours) is performed to improve the stability and sensitivity of the resistance.

[0080] S2, flexible circuit board integration: A flexible circuit board (FPC) with a three-dimensional structure is designed and manufactured, a polyimide (PI) film is used as a base material, and circuit wiring is manufactured on the PI film through processes such as photolithography and electroplating; the prepared glass micro-fusion strain gauge type sensor is accurately pasted on the corresponding position of the flexible circuit board through conductive silver paste (H20E, Sanjian Company, Japan), and packaging treatment is performed to protect the sensor from external environmental interference.

[0081] The embodiment realizes high-precision detection functions of three-axis force (range 0~500mN, precision 0.1%FS) and three-dimensional torque (range 0~10mN·m, precision 0.5% FS) through optimization of circuit design and layout, and can realize distributed signal acquisition through the flexible circuit board.

[0082] After force and torque tests, the six-dimensional force tactile array can accurately measure three-axis force and three-dimensional torque, with a force detection precision of 0.1%FS and a torque detection precision of 0.5% FS, which can meet the accurate perception needs of the ship carbon capture supergravity equipment to the small force and torque changes in the complex operation process, and provide accurate force feedback information for the operation and repair of nanorobots on the surface of the equipment. At the same time, due to the use of flexible circuit board integration technology, the tactile array has good flexibility and adaptability, and can adapt to the fitting and detection needs of nanorobots on the surface of complex-shaped equipment. In the case of a bending radius of 5mm, the sensor performance remains stable and the signal transmission is normal.

[0083] In the embodiment, the positioning sensing module (quantum dot fluorescence positioning sensor) is prepared including the following steps: S1, surface modification of carbon nanotube-graphene aerogel: A carbon nanotube-graphene composite structure is grown on a silicon wafer substrate at a mass ratio of 1:3~1:5 under high temperature (800℃) and hydrogen / methane mixed gas (volume ratio 5:1) environment by chemical vapor deposition (CVD) method, and after ultrasonic dispersion into a solution of 2~5mg / mL, 0.5~1wt% chitosan is crosslinked, and a porous aerogel is prepared after drying; The surface of the aerogel is subjected to amination treatment, the aerogel is soaked in a 1~3 wt% 3-aminopropyltrimethoxysilane (APTMS) ethanol solution (ethanol concentration 95vol%) at a mass ratio of 1:100~1:200, and the amination treatment is completed after stirring at 60℃ for 12~24 hours, so that the surface of the aerogel is grafted with amino functional groups to provide active sites for subsequent quantum dot loading. Finally, the aerogel is washed with ethanol and vacuum dried.

[0084] S2, CdSe quantum dot / MXene heterostructure construction: CdSe quantum dots with an emission wavelength of 525 nm were synthesized and loaded on the surface of aminated carbon nanotube-graphene aerogel by electrostatic adsorption, with a loading capacity of 0.5 mg / cm 2 Then, a 5-nm-thick Ti3C2Tx MXene layer was deposited on the surface of the quantum dot-loaded aerogel using atomic layer deposition (ALD) technology, and a fluorescence resonance energy transfer (FRET) system was constructed using the fluorescence quenching properties of MXene.

[0085] During the ALD deposition process, the pulse time and flow rate of TiCl4 and H2O were precisely controlled to ensure the uniformity and thickness accuracy of the MXene layer.

[0086] In this embodiment, the quantum dot fluorescence positioning sensor has excellent performance, with nanoscale microcrack positioning accuracy and high response speed. The quantum dot fluorescence positioning system can achieve nanoscale positioning of microcracks using the FRET effect, with a resolution of up to 50 nm. When a microcrack appears on the surface of the device, the stress and strain changes around the crack will cause changes in the distance and interaction between the quantum dots and MXene, resulting in changes in the fluorescence signal. Through precise detection and analysis of the fluorescence signal, the position and size of the microcrack can be accurately determined, providing key information for the timely and accurate repair of the nanorobot. Moreover, the response time of the positioning system is less than 200 ms, allowing it to quickly detect and feedback signals the instant a microcrack appears on the surface of the device, enabling the nanorobot to respond quickly and repair the device in a timely manner, effectively preventing the further expansion and deterioration of the microcrack.

[0087] Furthermore, in this embodiment, the TiO2 / Pt heterojunction PS module based on the Janus nanomotor serves as the driving module, and its preparation method includes the following steps: S1, preparing a TiO2 / Pt heterojunction using ALD technology: Polystyrene (PS) microspheres (particle size 500 nm) were used as templates, and a double-metal layer was deposited on the surface of the PS microspheres using atomic layer deposition (ALD) technology.

[0088] First, the PS microspheres were placed in the ALD reaction chamber, and TiCl4 and H2O were introduced as precursors to perform ALD reactions at a temperature of 150°C. By precisely controlling the pulse time and cycle number of TiCl4 and H2O, a 5-nm-thick TiO2 layer was deposited. Then, the precursors were switched to Pt (acac)2 and O2, and ALD reactions were continued at a temperature of 250°C to deposit a 3-nm-thick Pt layer, forming a TiO2 / Pt heterostructure. Finally, the PS microsphere template was removed by O2 plasma etching, resulting in Janus nanoparticles with a TiO2 / Pt heterostructure.

[0089] In this embodiment, during the atomic layer deposition of the bimetallic layer, the mass ratio of the polystyrene microsphere template to the precursor and the process parameters are as follows: the polystyrene microspheres are placed in the reaction cavity, TiCl4 and another metal precursor (for example, AlCl3) are used as the bimetallic source, the mass ratio of the two is controlled at 1:0.8-1:1.2 (for example, 0.5 g of TiCl4 corresponds to 0.4-0.6 g of AlCl3), and the mass ratio of the two to the microspheres is 0.5:100-1:100. H2O is introduced as the reaction gas, and deposition is carried out in a pulse mode at 150°C, the single pulse mass ratio of TiCl4 to H2O is about 1:0.05, and the thickness of the bimetallic layer is controlled by the number of cycles. Finally, the composite structure is obtained by removing the template.

[0090] In this embodiment, during the ALD reaction, the uniformity and thickness precision of the bimetallic layer are ensured by strictly controlling the reaction temperature, precursor flow rate, and pulse time, etc.

[0091] S2, surface modification and performance optimization: The prepared Janus nanoparticles are surface modified, and mercaptopropionic acid (MPA) is used for functionalization treatment to introduce carboxyl functional groups on the surface of the Janus nanoparticles, so as to improve the dispersibility and stability of the Janus nanoparticles in aqueous solution. By optimizing the surface modification conditions, the dispersion stability of the Janus nanoparticles in 3.5% NaCl solution is improved by 80%, and no obvious aggregation phenomenon occurs within 100 hours of testing time.

[0092] The driving module prepared in this embodiment has good photothermal-chemical driving ability and endurance. It combines photothermal driving and chemical driving to form a powerful multi-field coupling driving system. After detection, the driving speed of the driving module under 808 nm laser irradiation can reach 3.5 μm / s, the TiO2 hemisphere of the TiO2 / Pt Janus nanoparticle can efficiently absorb light energy and convert it into heat energy, generating a local high temperature (ΔT=30°C), driving the surrounding H2O2 to decompose and generate directional bubbles to propel, and after optimization, the driving force reaches 5 nN, which is 67% higher than that of traditional Janus particles, and can provide strong power for the movement of nanorobots on the surface of ship carbon capture supergravity equipment. Moreover, by optimizing the material structure and reaction conditions, the endurance time of the Janus nano-engine in H2O2 solution reaches 120 hours, which is significantly improved compared with the traditional driving mode, and can meet the driving needs of nanorobots in long-time complex tasks.

[0093] Furthermore, the nanorobot realizes self-energy supply by using a chemical self-energy supply module. The construction of the chemical self-energy supply module includes the following steps: S1, integration of cascade reaction module Glucose oxidase (GO x ) and catalase (CAT) are immobilized on the surface of nanoporous materials (such as mesoporous silica with a pore size of 20 nm) in turn by layer-by-layer self-assembly technology.

[0094] First, the mesoporous silica nanoparticles are immersed in a phosphate buffer solution (PBS, pH = 7.4) containing GO x , and GO x is loaded on the surface of the mesoporous silica by physical adsorption, with a loading amount of 1 mg / m 2 ; then, the GO x -loaded mesoporous silica nanoparticles are immersed in a PBS solution containing CAT, and CAT is further immobilized on the surface by electrostatic interaction and cross-linking reaction, forming a stable glucose oxidase-catalase cascade reaction system.

[0095] The system can continuously generate H2O2 using glucose and O2 in the ship environment to provide chemical driving force for the Janus nanomotor.

[0096] S2, self-powered module packaging and integration: The constructed glucose oxidase-catalase cascade reaction system is packaged and integrated with the Janus nanomotor, and a high-molecular-weight film (such as a polyether sulfone film with a molecular weight cutoff of 10,000 Da) with selective permeability is used to package the reaction system, which can ensure the entry of glucose and O2, and prevent enzyme leakage and external impurities interference.

[0097] By optimizing the packaging process and materials, the output power of the self-powered module reaches 0.5 muW / cm², which can provide continuous and stable energy supply for the driving of the nanorobot.

[0098] The present application can realize self-powered driving of the nanorobot under the condition of the existence of external specific chemicals by increasing the cascade reaction module, and improve the environmental adaptability of the nanorobot.

[0099] The chemical self-powered module can continuously utilize glucose and O2 in the ship environment to generate H2O2, and provide stable chemical driving force for the Janus nano engine, so that the nano robot can be autonomously operated for a long time without external power supply, the self-powered driving capability is improved compared with the traditional battery power supply mode, and the working time and application range of the nano robot are effectively prolonged. Moreover, in the complex environment of ship operation, including under different temperature (-20 DEG C ~ 60 DEG C), humidity (20% ~ 90%) and salinity (0 ~ 3.5% NaCl), the self-powered module can maintain stable performance, the output power fluctuation is small, 10%, which can adapt to various harsh environments of the ship carbon capture supergravity equipment, and ensure the reliable operation of the nano robot.

[0100] The application discloses a nano self-repairing coating robot applied to a ship carbon capture supergravity equipment based on multi-field coupling driving and a preparation method thereof.

[0101] In the description of the present application, it should be understood that the orientation or positional relationship indicated by terms such as "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present application and simplifying the description, and does not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation of the present application.

[0102] In addition, the terms "first", "second" are only for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "multiple" is two or more, unless otherwise specifically limited.

[0103] The above only describes preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A nanoremediation coating robot characterized by, The functional layer is a substrate layer, and the driving layer is arranged on the surface of the functional layer; The functional layer includes a hollow core-shell provided with a gap and a repair unit and a copolymer layer polymerized on the hollow core-shell, and the repair unit includes an NH2-MXene repair unit; The driving layer includes a base material module and a force sensing module, a positioning sensing module, and a driving module integrated on the base material module.

2. A nanoremediation coating robot according to claim 1, wherein, The hollow core-shell is composed of a gel matrix of Al2O3@SiO2 particles, and the gap is filled with the repair unit; the copolymer layer is a PLGA-b-PNIPAM block copolymer layer, which covers the gap of the hollow core-shell and adjusts the hydrogen bond strength at the SiO2 interface of the block polymer through temperature response; and the Al2O3@SiO2 is used as the shell, the PNIPAM block copolymer is used as the cover, and the NH2-MXene repair unit is used as the content to prepare a core-shell structure microcapsule. The base material module includes a high-purity borosilicate glass layer, the force sensing module includes a flexible circuit board PI layer arranged on the upper part of the high-purity borosilicate glass layer, the positioning sensing module includes a carbon nanotube-graphene gel layer, and the driving module includes a TiO2 / Pt heterojunction PS layer.

3. A nano self-healing coating robot according to claim 2, wherein, The Al2O3@SiO2 hollow core-shell is synthesized by a sol-gel method, and the preparation includes the following steps: 1g of Al2O3 nanoparticles with a particle size of 50nm are uniformly dispersed in 100 mL of an ethanol solvent, then 2g of tetraethyl orthosilicate and 0.1g of 25wt% ammonia water are added, and the reaction is carried out at a temperature of 60°C for 4 hours to form a SiO2 shell layer on the surface of the Al2O3 nanoparticles through a sol-gel process; After the reaction is completed, the product is calcined at 500°C for 2 hours to solidify the SiO2 shell layer, and Al2O3@SiO2 hollow core-shell particles with a particle size of 80nm and a shell thickness of 15nm are obtained.

4. A nano self-healing coating robot according to claim 3, wherein, The prepared Al2O3@SiO2 hollow core-shell particles are loaded with a DOPA-TA composite coating, and the loading process is as follows: The prepared Al2O3@SiO2 hollow core-shell particles are dispersed in a Tris-HCl buffer solution with a pH value of 8.5, 100mg of dopamine with a concentration of 1mg / mL and 135mg of tannic acid with a concentration of 1.35mg / mL are sequentially added to the 100mL system, and the system is stirred at room temperature for 24 hours, so that dopamine and tannic acid are self-assembled on the surface of the Al2O3@SiO2 particles to form a uniform composite coating through hydrogen bonding and electrostatic interaction.

5. A nano self-healing coating robot according to claim 2, wherein, The repair unit includes a double-network hydrogel matrix and a MXene nanoplatelet reinforcing phase, the double-network hydrogel matrix uses a PAAm / PAA double-network hydrogel as a precursor, and the preparation of the double-network hydrogel matrix includes the following steps: S1, synthesis of a first network hydrogel: The acrylamide monomer and N,N'-methylene bisacrylamide are dissolved in deionized water in a mass ratio of 3:2 to maintain a solid content of 15%, oxygen in the system is excluded, and then 0.1% of ammonium persulfate and 0.05% of tetramethyl ethylenediamine are added to the system, and the polymerization reaction is initiated; the reaction system is placed in a constant temperature water bath at 60°C, and the reaction is continued for 4 hours to prepare the PAAm network hydrogel; S2, synthesis of the second network hydrogel: The acrylamide monomer and 0.5 wt % of N,N'-methylene bisacrylamide are uniformly mixed, 1.5 M sodium hydroxide solution is added, the pH value of the solution is adjusted to 7.0, and 0.3 wt % of ammonium persulfate is added to the reaction system as a free radical polymerization initiator at a temperature of 68-73°C, and the reaction is continued for 6 hours to prepare the PAA network hydrogel. S3, formation of the interpenetrating network: The prepared PAA network hydrogel is soaked in an aqueous solution containing 10 wt % acrylamide monomer, 0.1 wt % N,N'-methylene bisacrylamide crosslinking agent, and 0.2 wt % ammonium persulfate initiator, and swelled at 30°C for 24 hours to allow the hydrogel to fully absorb the monomer solution, and then the system is heated to 68-73°C and reacted for 6 hours to initiate in-situ polymerization of acrylamide inside the PAAm network to form an interpenetrating polymer network hydrogel.

6. A nano self-healing coating robot according to claim 5, wherein, Preparation of the MXene nanoplatelet reinforcing phase includes the following steps: S1, raw material pretreatment First, Ti3C2Tx MXene is prepared by HF etching, and then ultrasonic stripping treatment is performed to disperse the MXene platelets, and pure MXene platelets are collected by centrifugation; S2, surface grafting reaction The collected MXene platelets are uniformly dispersed in a 3-aminopropyltrimethoxysilane solution containing 5 vol% ethanol, 1-3 grams of 3-aminopropyltrimethoxysilane are added per gram of MXene, and the 3-aminopropyltrimethoxysilane is dissolved in an appropriate amount of 5 vol% ethanol solution, 75 mL of solution is added per gram of MXene, the pH value of the solution is adjusted to 4.5, and the reaction is continued to graft amino functional groups onto the surface of the MXene using an amidation reaction; S3, post-treatment After the reaction is completed, the product is washed repeatedly with deionized water until it is neutral, and unreacted substances and impurities are removed, and the modified NH2-MXene repair unit is obtained by freeze-drying.

7. A nano self-healing coating robot according to claim 2, wherein, The preparation of the copolymer layer includes the following steps: D,L-lactide and N-isopropyl acrylamide are dissolved in toluene solvent in a molar ratio of 50:30 to form a solution with a total monomer concentration of 1.0 mol / L, and then 0.05 wt % of stannous octoate is added as a catalyst, and the reaction is continued for 24 hours at a temperature of 110°C to synthesize an amphiphilic block copolymer by ring-opening polymerization.

8. A nano self-healing coating robot according to claim 2, wherein, The core-shell interface polymerization is performed using a thiol-ene click reaction, including the following steps: A thiol-containing silane coupling agent is grafted onto the surface of SiO2 by hydrosilylation to form an active interface with a decreasing density of thiol groups from the edge to the center; Preparation of end-functionalized PLGA by reversible addition-fragmentation chain transfer polymerization 100 -b-PNIPAM 50 The block copolymer, wherein the PLG segment is as a hydrophobic anchor segment of the SiO2 surface, the PNIPAM segment is as a temperature-sensitive response segment, the edge region has a higher grafting density than the center region, forming a gradient graft network with edge-rich and center-sparse.

9. A nano self-healing coating robot according to claim 2, wherein, The preparation of the force sensing module includes the following steps: A 5-micron wide and 50-micron long resistance pattern is photoetched on a high-purity borosilicate glass substrate by using an electron beam lithography technique, and then a wet etching process is used to remove the excess glass material to form a resistance structure; A 200-nm-thick nickel-chromium alloy layer is deposited on the resistance surface as a sensitive material by using a magnetron sputtering technique, and then high-temperature annealing is performed; The positioning sensing module preparation comprises the following steps: A carbon nanotube-graphene composite structure is grown on a silicon wafer substrate at a mass ratio of 1:3 to 1:5, and after ultrasonic dispersion into a solution of 2 to 5 mg / mL, 0.5 to 1 wt% chitosan is crosslinked to prepare a gas gel with a porous structure; then the surface of the gas gel is subjected to amination treatment, and the gas gel is soaked in a 1 to 3 wt% 3-aminopropyltrimethoxysilane ethanol solution at a mass ratio of 1:100 to 1:200; CdSe quantum dots are synthesized and loaded on the surface of the aminated carbon nanotube-graphene aerogel by electrostatic adsorption, and then a Ti3C2Tx MXene layer is deposited on the surface of the quantum dot-loaded aerogel to construct a fluorescence resonance energy transfer system.

10. A nano self-healing coating robot according to claim 2, wherein, The driving module preparation method comprises the following steps: S1, using polystyrene microspheres as templates, a double-metal layer is deposited on the surface of the polystyrene microspheres by atomic layer deposition technology, the polystyrene microspheres are placed in an atomic layer deposition reaction chamber, TiCl4 and H2O are introduced as precursors, the mass ratio of the double-metal source is 1:0.8 to 1:1.2, the mass ratio of the double-metal source to the microspheres is 0.5:100 to 1:100, and the atomic layer deposition reaction is carried out at a temperature of 150 DEG C; S2, switching the precursors to Pt(acac)2 and O2, and continuing the atomic layer deposition reaction at a temperature of 250 DEG C to form a TiO2 / Pt heterostructure; S3, removing the polystyrene microsphere template by O2 plasma etching to obtain Janus nanoparticles with a TiO2 / Pt heterostructure.

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