CN108864780B - Anti-cracking inorganic hole sealing agent - Google Patents
Anti-cracking inorganic hole sealing agent Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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Abstract
The invention discloses an anti-cracking inorganic hole sealing agent, and belongs to the technical field of material corrosion and protection. Weighing the following components in parts by weight: 70-100 parts of water glass, 15-20 parts of sodium fluosilicate, 10-18 parts of mica, 10-15 parts of modified graphene oxide, 10-15 parts of modified polyvinyl alcohol fiber, 8-12 parts of modified carbon nano tube and 5-8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 30-40 min at the temperature of 40-50 ℃ and the rotating speed of 300-400 r/min to obtain the cracking-resistant inorganic hole sealing agent. The anti-cracking inorganic hole sealing agent prepared by the technical scheme of the invention has the characteristic of excellent toughness, and has wide prospects in the development of material corrosion and protection technology industries.
Description
Technical Field
The invention discloses an anti-cracking inorganic hole sealing agent, and belongs to the technical field of material corrosion and protection.
Background
For many thermal spray coatings, sealing is a necessary post-treatment process. When the coating is exposed to corrosive and oxidative (sometimes high temperature) environments, sealing is a matter of design consideration. Any thermal spray process, particularly gas-oxygen flame spraying (i.e., flame spraying), deposits a coating having a porous structure. Overall, the range of coating porosity is quite large. Gas-oxygen flame sprayed layers are sometimes as high as 15% or more, while high velocity oxygen-gas sprayed (HVOF) layers are below 1%. In practical applications, a porous structure is sometimes advantageous. The coating pores are beneficial to storing oil, promoting lubrication and reducing abrasion; in some particular applications, porous materials are formed by thermal spraying for use in heat exchange devices or other components. However, in more cases, porosity of the coating is undesirable. When the coating is exposed to atmosphere, steam, industrial atmosphere, chemical active substances, corrosive gas and high-temperature environment, corrosive elements are introduced into pores, so that the coating and a substrate are subjected to chemical or electrochemical corrosion, and the coating fails, and in such a case, the coating needs to be sealed.
As a post-treatment process of thermal spraying, the main content of the sealing operation is selection of a sealing agent and a construction method. If some workpieces need turning or grinding after being sprayed, hole sealing is carried out before the workpiece, so that coating pores are prevented from being polluted, and better and cleaner grinding finish is guaranteed. When the sprayed ceramic coating is used for insulation, the sealing can maintain the dielectric constant of the coating. Otherwise, the pores of the coating will absorb moisture or become contaminated, forming undesirable conductive pathways in the coating. In addition, for equipment such as a pump or a hydraulic machine, sealing holes also prevent sealing leakage of liquid and pressure.
The traditional sealant has the problem of easy cracking caused by poor toughness, so that an ideal effect cannot be achieved in the use process, and therefore, the problem that how to improve the toughness of the traditional sealant cannot be further improved is to be solved.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the defect that the traditional sealant is easy to crack due to poor toughness, the cracking-resistant inorganic sealant is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an anti-cracking inorganic hole sealing agent is composed of the following raw materials in parts by weight: 70-100 parts of water glass, 15-20 parts of sodium fluosilicate and 10-18 parts of mica, wherein the anti-cracking inorganic hole sealing agent further comprises: 10-15 parts of modified graphene oxide, 10-15 parts of modified polyvinyl alcohol fibers, 8-12 parts of modified carbon nanotubes and 5-8 parts of additives;
the preparation method of the modified graphene oxide comprises the following steps:
mixing graphene oxide and petroleum ether according to a mass ratio of 1: 150-1: 200, adding paraffin dispersion liquid with the mass 5-10 times that of graphene oxide after ultrasonic dispersion, stirring and reacting, performing rotary evaporation and concentration, and performing vacuum drying to obtain a modified graphene oxide blank, wherein the modified graphene oxide blank and nitric acid are mixed according to a mass ratio of 1: 8-1: 12, mixing and filtering to obtain modified graphene oxide;
the preparation method of the modified polyvinyl alcohol fiber comprises the following steps:
mixing a polyvinyl alcohol solution and a graphene oxide solution according to a volume ratio of 5: 1-8: 1, mixing, stirring and mixing, performing electrostatic spinning, and drying to obtain modified polyvinyl alcohol fibers;
the preparation method of the modified carbon nano tube comprises the following steps:
mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 280-1: 300, mixing, performing ultrasonic dispersion, adjusting the pH value to 8-10, stirring for reaction, adjusting the pH value to be neutral, performing suction filtration and washing, and performing vacuum drying to obtain a pre-modified carbon nano tube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 200-1: 280, mixing, performing ultrasonic dispersion, adding ammonia water which is 5-8 times of the mass of the pre-modified carbon nano tube and an ethyl orthosilicate mixture which is 10-30 times of the mass of the pre-modified carbon nano tube, performing ultrasonic dispersion, stirring for reaction to obtain a modified carbon nano tube mixture, and mixing the modified carbon nano tube mixture and a silane coupling agent mixture according to a mass ratio of 20: 1-40: 1, mixing, filtering, drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with hydrochloric acid according to a mass ratio of 1: 5-1: 8, mixing and filtering to obtain modified carbon nanotubes;
the preparation method of the additive comprises the following steps:
mixing gelatin microspheres and boric acid solution according to the mass ratio of 1: 6-1: 10, adjusting the pH value to 2.3-2.5, stirring and mixing, adjusting the pH value to 4.8-5.8, and filtering to obtain the additive.
The paraffin dispersion liquid is prepared by mixing paraffin with 24-32 carbon atoms and petroleum ether according to a mass ratio of 1: 10-1: 12 mixing to obtain paraffin dispersion
The electrostatic spinning conditions are that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning solution is 0.3 mL/h.
The ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution.
The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 15-1: 20 to obtain an ethyl orthosilicate mixture.
The silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.4-0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture.
The gelatin microspheres are sequentially weighed according to parts by weight: 100-120 parts of polyvinyl alcohol, 60-80 parts of gelatin, 300-450 parts of water, 30-50 parts of glutaraldehyde aqueous solution and 10-30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, and vacuum drying to obtain the gelatin microspheres.
The modulus of the water glass is 2.6-2.8.
The invention has the beneficial effects that:
(1) according to the invention, the modified carbon nano tube is added when the anti-cracking inorganic hole sealing agent is prepared, firstly, the surface of the modified carbon nano tube is grafted with silicon dioxide, and after the modified carbon nano tube is added into a product, the silicon dioxide can be dispersed in the product to a certain extent under the action of a silane coupling agent, so that the agglomeration of the carbon nano tube is prevented, and further the toughness of the product is improved;
(2) according to the invention, the modified polyvinyl alcohol fiber and the additive are added when the anti-cracking inorganic hole sealing agent is prepared, on one hand, the graphene oxide is added into the modified polyvinyl alcohol fiber, and can be combined with the modified carbon nanotube through electrostatic adsorption in the using process of a product, so that a complex three-dimensional network is formed in the product, and the toughness of the product is improved, on the other hand, the added additive contains microspheres sensitive to pH, and after the additive is added into the product, the pH of the product is improved along with the solidification and crosslinking of sodium silicate, so that boric acid solution in the additive is released, the modified polyvinyl alcohol fiber is crosslinked, the crosslinking degree in the product is improved, and the toughness of the product is improved.
Detailed Description
Weighing the following components in parts by weight: 100-120 parts of polyvinyl alcohol, 60-80 parts of gelatin, 300-450 parts of water, 30-50 parts of a glutaraldehyde aqueous solution with the mass fraction of 22-28% and 10-30 parts of hydrochloric acid with the mass fraction of 32-38%, mixing the polyvinyl alcohol with the water, stirring for 45-80 min at the temperature of 85-95 ℃ and the rotating speed of 220-300 r/min to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution to 50-70 ℃, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid with the mass fraction of 32-38% and the glutaraldehyde aqueous solution with the mass fraction of 22-28% into the mixture of the polyvinyl alcohol solution and the gelatin, stirring and mixing for 10-12 h at the temperature of 28-38 ℃ and the rotating speed of 250-300 r/min, filtering to obtain a pretreated gel, cutting the pretreated gel into blocks, washing for 5-6 days by using deionized water, changing deionized water every 10-12 h, vacuum drying the washed gel block for 3-5 h at room temperature to obtain gelatin microspheres, and mixing graphene oxide and petroleum ether according to a mass ratio of 1: 150-1: 200, mixing the mixture in a beaker, performing ultrasonic dispersion for 30-40 min under the condition of the frequency of 55-65 kHz, adding paraffin dispersion liquid with the mass 5-10 times of that of graphene oxide into the beaker, stirring and reacting for 60-80 min under the conditions of the temperature of 65-70 ℃ and the rotating speed of 300-400 r/min, performing rotary evaporation and concentration on the materials in the beaker for 2-3 h under the conditions of the temperature of 70-80 ℃, the rotating speed of 120-150 r/min and the pressure of 500-600 kPa to obtain a concentrate, performing vacuum drying on the concentrate for 2-3 h under the condition of 50-60 ℃ to obtain a modified graphene oxide blank, and mixing the modified graphene oxide blank with 20-30% nitric acid according to the mass ratio of 1: 8-1: 12, mixing, standing for 30-40 min at room temperature, and filtering to obtain modified graphene oxide; mixing a polyvinyl alcohol aqueous solution with the mass fraction of 5-7% and a graphene oxide solution with the mass fraction of 1-3% according to the volume ratio of 5: 1-8: 1, mixing, stirring and mixing for 1-2 hours at the temperature of 45-55 ℃ and the rotating speed of 300-400 r/min under the conditions of 85-90 ℃ and the rotating speed of 300-400 r/min, carrying out electrostatic spinning to obtain pretreated modified polyvinyl alcohol fibers, and carrying out vacuum drying on the pretreated modified polyvinyl alcohol fibers at the temperature of 50-55 ℃ for 10-12 hours to obtain modified polyvinyl alcohol fibers; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 280-1: 300, mixing the mixture in a flask, performing ultrasonic dispersion for 30-40 min under the condition of the frequency of 45-55 kHz, adjusting the pH of materials in the flask to 8-10 by using a potassium hydroxide solution with the mass fraction of 15-20%, stirring and reacting for 8-9 h under the conditions that the temperature is 85-90 ℃ and the rotating speed is 300-400 r/min, adjusting the pH of the materials in the flask to be neutral by using hydrochloric acid with the mass fraction of 10-18%, performing suction filtration and water washing to obtain a pre-modified carbon nanotube blank, and performing vacuum drying on the pre-modified carbon nanotube blank for 4-5 h under the condition that the temperature is 70-75 ℃ to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 200-1: 280, mixing the mixture in a conical flask, performing ultrasonic dispersion for 60-70 min under the condition of the frequency of 45-60 kHz, adding ammonia water with the mass fraction of 25-28% and an ethyl orthosilicate mixture with the mass fraction of 10-30 times of the mass of the pre-modified carbon nano tube, wherein the mass fraction of the ammonia water is 5-8 times of the mass of the pre-modified carbon nano tube, into the conical flask, performing ultrasonic dispersion for 50-60 min under the condition of the frequency of 45-60 kHz, stirring and reacting for 18-20 h under the conditions that the temperature is 30-40 ℃ and the rotating speed is 250-350 r/min to obtain a modified carbon nano tube mixture, and mixing the modified carbon nano tube mixture with a silane coupling agent mixture according to the mass ratio of 20: 1-40: 1, mixing, stirring and mixing for 15-20 min at the temperature of 30-40 ℃ and the rotating speed of 300-400 r/min, performing suction filtration and drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with 10-18% hydrochloric acid in a mass ratio of 1: 5-1: 8, mixing, soaking for 30-40 min at room temperature, and filtering to obtain modified carbon nanotubes; mixing gelatin microspheres with a boric acid solution with the mass fraction of 20-30% in a mass ratio of 1: 6-1: 10, regulating the pH value of a mixture of the gelatin microspheres and a boric acid solution to 2.3-2.5 by using hydrochloric acid with the mass fraction of 15-20%, stirring and mixing for 1-2 hours at the temperature of 40-50 ℃ and the rotating speed of 300-400 r/min, regulating the pH value of the mixture of the gelatin microspheres and the boric acid solution to 4.8-5.8 by using ammonia water with the mass fraction of 12-18%, and filtering to obtain an additive, wherein the additives are sequentially weighed according to the parts by weight: 70-100 parts of water glass, 15-20 parts of sodium fluosilicate, 10-18 parts of mica, 10-15 parts of modified graphene oxide, 10-15 parts of modified polyvinyl alcohol fiber, 8-12 parts of modified carbon nano tube and 5-8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 30-40 min at the temperature of 40-50 ℃ and the rotating speed of 300-400 r/min to obtain the cracking-resistant inorganic hole sealing agent. The paraffin dispersion liquid is prepared by mixing paraffin with 24-32 carbon atoms and petroleum ether according to a mass ratio of 1: 10-1: 12, and obtaining the paraffin dispersion liquid under the electrostatic spinning condition that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning liquid is 0.3 mL/h. The ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 15-1: 20 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.4-0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture. The modulus of the water glass is 2.6-2.8.
Example 1
Weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution with the mass fraction of 28% and 30 parts of hydrochloric acid with the mass fraction of 38%, mixing the polyvinyl alcohol with the water, stirring for 80min at the temperature of 95 ℃ and the rotating speed of 300r/min to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution to 70 ℃, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid with the mass fraction of 38% and the glutaraldehyde aqueous solution with the mass fraction of 28% into the mixture of the polyvinyl alcohol solution and the gelatin, stirring and mixing for 12h at the temperature of 38 ℃ and the rotating speed of 300r/min, filtering to obtain pretreated gel, cutting the pretreated gel into blocks, washing for 6 days by deionized water, changing the deionized water once every 12h, vacuum-drying the washed gel blocks for 5h at room temperature, obtaining gelatin microspheres, and mixing the graphene oxide and petroleum ether according to a mass ratio of 1: 200, mixing the mixture in a beaker, performing ultrasonic dispersion for 40min under the condition of 65kHz, adding paraffin dispersion liquid with the mass 10 times that of graphene oxide into the beaker, stirring and reacting for 80min under the conditions of 70 ℃ and 400r/min, performing rotary evaporation and concentration for 3h under the conditions of 80 ℃ and 600kPa on the materials in the beaker to obtain a concentrate, performing vacuum drying for 3h under the condition of 60 ℃ on the concentrate to obtain a modified graphene oxide blank, and mixing the modified graphene oxide blank with 30% nitric acid according to the mass ratio of 1: 12, mixing, standing for 40min at room temperature, and filtering to obtain modified graphene oxide; mixing a polyvinyl alcohol aqueous solution with the mass fraction of 7% and a graphene oxide solution with the mass fraction of 3% according to the volume ratio of 8: 1, mixing, stirring and mixing for 2 hours at the temperature of 55 ℃ and the rotating speed of 400r/min under the conditions of 90 ℃ and 400r/min, carrying out electrostatic spinning to obtain pretreated modified polyvinyl alcohol fibers, and carrying out vacuum drying on the pretreated modified polyvinyl alcohol fibers at the temperature of 55 ℃ for 12 hours to obtain the modified polyvinyl alcohol fibers; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300, mixing the mixture in a flask, performing ultrasonic dispersion for 40min under the condition of 55kHz, adjusting the pH of the material in the flask to 10 by using a potassium hydroxide solution with the mass fraction of 20%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min of rotation speed, adjusting the pH of the material in the flask to be neutral by using hydrochloric acid with the mass fraction of 18%, performing suction filtration and water washing to obtain a pre-modified carbon nanotube blank, and performing vacuum drying on the pre-modified carbon nanotube blank for 5h under the condition of 75 ℃ to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 280 are mixed in a conical flask, the mixture is subjected to ultrasonic dispersion for 70min under the condition of 60kHz, ammonia water with the mass fraction of 28 percent and tetraethoxysilane with the mass fraction of 30 percent are added into the conical flask, the mass fraction of the mixture is 8 times that of the pre-modified carbon nano tubes, the mixture is subjected to ultrasonic dispersion for 60min under the condition of 60kHz, the mixture is stirred and reacts for 20h under the conditions of 40 ℃ and 350r/min of rotation speed, a modified carbon nano tube mixture is obtained, and the modified carbon nano tube mixture and a silane coupling agent mixture are mixed according to the mass ratio of 40: 1, stirring and mixing for 20min at the temperature of 40 ℃ and the rotating speed of 400r/min, performing suction filtration and drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with 18% hydrochloric acid in a mass ratio of 1: 8, mixing, soaking for 40min at room temperature, and filtering to obtain modified carbon nanotubes; mixing gelatin microspheres with a boric acid solution with the mass fraction of 30% according to the mass ratio of 1: 10, regulating the pH value of a mixture of the gelatin microspheres and a boric acid solution to 2.5 by using hydrochloric acid with the mass fraction of 20%, stirring and mixing for 2 hours at the temperature of 50 ℃ and the rotating speed of 400r/min, regulating the pH value of the mixture of the gelatin microspheres and the boric acid solution to 5.8 by using ammonia water with the mass fraction of 18%, and filtering to obtain an additive, wherein the following components are weighed in sequence in parts by weight: 100 parts of water glass, 20 parts of sodium fluosilicate, 18 parts of mica, 15 parts of modified graphene oxide, 15 parts of modified polyvinyl alcohol fiber, 12 parts of modified carbon nano tube and 8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 40min under the conditions that the temperature is 50 ℃ and the rotating speed is 400r/min to obtain the anti-cracking inorganic hole sealing agent. The paraffin dispersion liquid is prepared by mixing paraffin with 32 carbon atoms and petroleum ether according to the mass ratio of 1: 12, and obtaining the paraffin dispersion liquid under the electrostatic spinning condition that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning liquid is 0.3 mL/h. The ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 20 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture. The modulus of the water glass is 2.8.
Example 2
Weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution with the mass fraction of 28% and 30 parts of hydrochloric acid with the mass fraction of 38%, mixing the polyvinyl alcohol with the water, stirring for 80min at the temperature of 95 ℃ and the rotating speed of 300r/min to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution to 70 ℃, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid with the mass fraction of 38% and the glutaraldehyde aqueous solution with the mass fraction of 28% into the mixture of the polyvinyl alcohol solution and the gelatin, stirring and mixing for 12h at the temperature of 38 ℃ and the rotating speed of 300r/min, filtering to obtain pretreated gel, cutting the pretreated gel into blocks, washing for 6 days by deionized water, changing the deionized water once every 12h, vacuum-drying the washed gel blocks for 5h at room temperature, obtaining gelatin microspheres, and mixing the graphene oxide and petroleum ether according to a mass ratio of 1: 200, mixing the mixture in a beaker, performing ultrasonic dispersion for 40min under the condition of 65kHz, stirring and reacting for 80min under the conditions of temperature of 70 ℃ and rotating speed of 400r/min, performing rotary evaporation and concentration on the material in the beaker for 3h under the conditions of temperature of 80 ℃, rotating speed of 150r/min and pressure of 600kPa to obtain a concentrate, performing vacuum drying on the concentrate for 3h under the condition of 60 ℃ to obtain a modified graphene oxide blank, and mixing the modified graphene oxide blank with 30 mass percent nitric acid according to the mass ratio of 1: 12, mixing, standing for 40min at room temperature, and filtering to obtain modified graphene oxide; mixing a polyvinyl alcohol aqueous solution with the mass fraction of 7% and a graphene oxide solution with the mass fraction of 3% according to the volume ratio of 8: 1, mixing, stirring and mixing for 2 hours at the temperature of 55 ℃ and the rotating speed of 400r/min under the conditions of 90 ℃ and 400r/min, carrying out electrostatic spinning to obtain pretreated modified polyvinyl alcohol fibers, and carrying out vacuum drying on the pretreated modified polyvinyl alcohol fibers at the temperature of 55 ℃ for 12 hours to obtain the modified polyvinyl alcohol fibers; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300, mixing the mixture in a flask, performing ultrasonic dispersion for 40min under the condition of 55kHz, adjusting the pH of the material in the flask to 10 by using a potassium hydroxide solution with the mass fraction of 20%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min of rotation speed, adjusting the pH of the material in the flask to be neutral by using hydrochloric acid with the mass fraction of 18%, performing suction filtration and water washing to obtain a pre-modified carbon nanotube blank, and performing vacuum drying on the pre-modified carbon nanotube blank for 5h under the condition of 75 ℃ to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 280 are mixed in a conical flask, the mixture is subjected to ultrasonic dispersion for 70min under the condition of 60kHz, ammonia water with the mass fraction of 28 percent and tetraethoxysilane with the mass fraction of 30 percent are added into the conical flask, the mass fraction of the mixture is 8 times that of the pre-modified carbon nano tubes, the mixture is subjected to ultrasonic dispersion for 60min under the condition of 60kHz, the mixture is stirred and reacts for 20h under the conditions of 40 ℃ and 350r/min of rotation speed, a modified carbon nano tube mixture is obtained, and the modified carbon nano tube mixture and a silane coupling agent mixture are mixed according to the mass ratio of 40: 1, stirring and mixing for 20min at the temperature of 40 ℃ and the rotating speed of 400r/min, performing suction filtration and drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with 18% hydrochloric acid in a mass ratio of 1: 8, mixing, soaking for 40min at room temperature, and filtering to obtain modified carbon nanotubes; mixing gelatin microspheres with a boric acid solution with the mass fraction of 30% according to the mass ratio of 1: 10, regulating the pH value of a mixture of the gelatin microspheres and a boric acid solution to 2.5 by using hydrochloric acid with the mass fraction of 20%, stirring and mixing for 2 hours at the temperature of 50 ℃ and the rotating speed of 400r/min, regulating the pH value of the mixture of the gelatin microspheres and the boric acid solution to 5.8 by using ammonia water with the mass fraction of 18%, and filtering to obtain an additive, wherein the following components are weighed in sequence in parts by weight: 100 parts of water glass, 20 parts of sodium fluosilicate, 18 parts of mica, 15 parts of modified graphene oxide, 15 parts of modified polyvinyl alcohol fiber, 12 parts of modified carbon nano tube and 8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 40min under the conditions that the temperature is 50 ℃ and the rotating speed is 400r/min to obtain the anti-cracking inorganic hole sealing agent. The ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 20 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture. The modulus of the water glass is 2.8.
Example 3
Weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution with the mass fraction of 28% and 30 parts of hydrochloric acid with the mass fraction of 38%, mixing the polyvinyl alcohol with the water, stirring for 80min at the temperature of 95 ℃ and the rotating speed of 300r/min to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution to 70 ℃, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid with the mass fraction of 38% and the glutaraldehyde aqueous solution with the mass fraction of 28% into the mixture of the polyvinyl alcohol solution and the gelatin, stirring and mixing for 12h at the temperature of 38 ℃ and the rotating speed of 300r/min, filtering to obtain pretreated gel, cutting the pretreated gel into blocks, washing for 6 days by deionized water, changing the deionized water once every 12h, vacuum-drying the washed gel blocks for 5h at room temperature, obtaining gelatin microspheres, and mixing the graphene oxide and petroleum ether according to a mass ratio of 1: 200, mixing the mixture in a beaker, performing ultrasonic dispersion for 40min under the condition of 65kHz, adding paraffin dispersion liquid with the mass 10 times that of graphene oxide into the beaker, stirring and reacting for 80min under the conditions of 70 ℃ and 400r/min, performing rotary evaporation and concentration for 3h under the conditions of 80 ℃ and 600kPa on the materials in the beaker to obtain a concentrate, performing vacuum drying for 3h under the condition of 60 ℃ on the concentrate to obtain a modified graphene oxide blank, and mixing the modified graphene oxide blank with 30% nitric acid according to the mass ratio of 1: 12, mixing, standing for 40min at room temperature, and filtering to obtain modified graphene oxide; mixing a polyvinyl alcohol aqueous solution with the mass fraction of 7% and a graphene oxide solution with the mass fraction of 3% according to the volume ratio of 8: 1, mixing, stirring and mixing for 2 hours at the temperature of 55 ℃ and the rotating speed of 400r/min under the conditions of 90 ℃ and 400r/min, carrying out electrostatic spinning to obtain pretreated modified polyvinyl alcohol fibers, and carrying out vacuum drying on the pretreated modified polyvinyl alcohol fibers at the temperature of 55 ℃ for 12 hours to obtain the modified polyvinyl alcohol fibers; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300, mixing the mixture in a flask, performing ultrasonic dispersion for 40min under the condition of 55kHz, adjusting the pH of the material in the flask to 10 by using a potassium hydroxide solution with the mass fraction of 20%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min of rotation speed, adjusting the pH of the material in the flask to be neutral by using hydrochloric acid with the mass fraction of 18%, performing suction filtration and water washing to obtain a pre-modified carbon nanotube blank, and performing vacuum drying on the pre-modified carbon nanotube blank for 5h under the condition of 75 ℃ to obtain a pre-modified carbon nanotube; placing the pre-modified carbon nano tube in a conical flask, carrying out ultrasonic dispersion for 70min under the condition of 60kHz, adding a mixture of ammonia water with the mass fraction of 28% and tetraethoxysilane with the mass fraction of 30 times of the pre-modified carbon nano tube, wherein the mass fraction of the mixture is 8 times that of the pre-modified carbon nano tube, into the conical flask, carrying out ultrasonic dispersion for 60min under the condition of 60kHz, stirring and reacting for 20h under the conditions that the temperature is 40 ℃ and the rotating speed is 350r/min to obtain a modified carbon nano tube mixture, and mixing the modified carbon nano tube mixture with a silane coupling agent mixture according to the mass ratio of 40: 1, stirring and mixing for 20min at the temperature of 40 ℃ and the rotating speed of 400r/min, performing suction filtration and drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with 18% hydrochloric acid in a mass ratio of 1: 8, mixing, soaking for 40min at room temperature, and filtering to obtain modified carbon nanotubes; mixing gelatin microspheres with a boric acid solution with the mass fraction of 30% according to the mass ratio of 1: 10, regulating the pH value of a mixture of the gelatin microspheres and a boric acid solution to 2.5 by using hydrochloric acid with the mass fraction of 20%, stirring and mixing for 2 hours at the temperature of 50 ℃ and the rotating speed of 400r/min, regulating the pH value of the mixture of the gelatin microspheres and the boric acid solution to 5.8 by using ammonia water with the mass fraction of 18%, and filtering to obtain an additive, wherein the following components are weighed in sequence in parts by weight: 100 parts of water glass, 20 parts of sodium fluosilicate, 18 parts of mica, 15 parts of modified graphene oxide, 15 parts of modified polyvinyl alcohol fiber, 12 parts of modified carbon nano tube and 8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 40min under the conditions that the temperature is 50 ℃ and the rotating speed is 400r/min to obtain the anti-cracking inorganic hole sealing agent. The paraffin dispersion liquid is prepared by mixing paraffin with 32 carbon atoms and petroleum ether according to the mass ratio of 1: 12, and obtaining the paraffin dispersion liquid under the electrostatic spinning condition that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning liquid is 0.3 mL/h. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 20 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture. The modulus of the water glass is 2.8.
Example 4
Weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution with the mass fraction of 28% and 30 parts of hydrochloric acid with the mass fraction of 38%, mixing the polyvinyl alcohol with the water, stirring for 80min at the temperature of 95 ℃ and the rotating speed of 300r/min to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution to 70 ℃, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid with the mass fraction of 38% and the glutaraldehyde aqueous solution with the mass fraction of 28% into the mixture of the polyvinyl alcohol solution and the gelatin, stirring and mixing for 12h at the temperature of 38 ℃ and the rotating speed of 300r/min, filtering to obtain pretreated gel, cutting the pretreated gel into blocks, washing for 6 days by deionized water, changing the deionized water once every 12h, vacuum-drying the washed gel blocks for 5h at room temperature, obtaining gelatin microspheres, and mixing the graphene oxide and petroleum ether according to a mass ratio of 1: 200, mixing the mixture in a beaker, performing ultrasonic dispersion for 40min under the condition of 65kHz, adding paraffin dispersion liquid with the mass 10 times that of graphene oxide into the beaker, stirring and reacting for 80min under the conditions of 70 ℃ and 400r/min, performing rotary evaporation and concentration for 3h under the conditions of 80 ℃ and 600kPa on the materials in the beaker to obtain a concentrate, performing vacuum drying for 3h under the condition of 60 ℃ on the concentrate to obtain a modified graphene oxide blank, and mixing the modified graphene oxide blank with 30% nitric acid according to the mass ratio of 1: 12, mixing, standing for 40min at room temperature, and filtering to obtain modified graphene oxide; mixing a polyvinyl alcohol aqueous solution with the mass fraction of 7% and a graphene oxide solution with the mass fraction of 3% according to the volume ratio of 8: 1, mixing, stirring and mixing for 2 hours at the temperature of 55 ℃ and the rotating speed of 400r/min under the conditions of 90 ℃ and 400r/min, carrying out electrostatic spinning to obtain pretreated modified polyvinyl alcohol fibers, and carrying out vacuum drying on the pretreated modified polyvinyl alcohol fibers at the temperature of 55 ℃ for 12 hours to obtain the modified polyvinyl alcohol fibers; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300, mixing the mixture in a flask, performing ultrasonic dispersion for 40min under the condition of 55kHz, adjusting the pH of the material in the flask to 10 by using a potassium hydroxide solution with the mass fraction of 20%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min of rotation speed, adjusting the pH of the material in the flask to be neutral by using hydrochloric acid with the mass fraction of 18%, performing suction filtration and water washing to obtain a pre-modified carbon nanotube blank, and performing vacuum drying on the pre-modified carbon nanotube blank for 5h under the condition of 75 ℃ to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 280 are mixed in a conical flask, and are subjected to ultrasonic dispersion for 70min under the condition of 60kHz, ammonia water with the mass fraction of 28 percent and the mass of 8 times of the mass of the pre-modified carbon nano tube is added into the conical flask, and are subjected to ultrasonic dispersion for 60min under the condition of 60kHz, and are stirred and react for 20h under the conditions of 40 ℃ and 350r/min of rotation speed, so that a modified carbon nano tube mixture is obtained, and the modified carbon nano tube mixture and a silane coupling agent mixture are mixed according to the mass ratio of 40: 1, stirring and mixing for 20min at the temperature of 40 ℃ and the rotating speed of 400r/min, performing suction filtration and drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with 18% hydrochloric acid in a mass ratio of 1: 8, mixing, soaking for 40min at room temperature, and filtering to obtain modified carbon nanotubes; mixing gelatin microspheres with a boric acid solution with the mass fraction of 30% according to the mass ratio of 1: 10, regulating the pH value of a mixture of the gelatin microspheres and a boric acid solution to 2.5 by using hydrochloric acid with the mass fraction of 20%, stirring and mixing for 2 hours at the temperature of 50 ℃ and the rotating speed of 400r/min, regulating the pH value of the mixture of the gelatin microspheres and the boric acid solution to 5.8 by using ammonia water with the mass fraction of 18%, and filtering to obtain an additive, wherein the following components are weighed in sequence in parts by weight: 100 parts of water glass, 20 parts of sodium fluosilicate, 18 parts of mica, 15 parts of modified graphene oxide, 15 parts of modified polyvinyl alcohol fiber, 12 parts of modified carbon nano tube and 8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 40min under the conditions that the temperature is 50 ℃ and the rotating speed is 400r/min to obtain the anti-cracking inorganic hole sealing agent. The paraffin dispersion liquid is prepared by mixing paraffin with 32 carbon atoms and petroleum ether according to the mass ratio of 1: 12, and obtaining the paraffin dispersion liquid under the electrostatic spinning condition that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning liquid is 0.3 mL/h. The ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution. The silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture. The modulus of the water glass is 2.8.
Example 5
Weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution with the mass fraction of 28% and 30 parts of hydrochloric acid with the mass fraction of 38%, mixing the polyvinyl alcohol with the water, stirring for 80min at the temperature of 95 ℃ and the rotating speed of 300r/min to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution to 70 ℃, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid with the mass fraction of 38% and the glutaraldehyde aqueous solution with the mass fraction of 28% into the mixture of the polyvinyl alcohol solution and the gelatin, stirring and mixing for 12h at the temperature of 38 ℃ and the rotating speed of 300r/min, filtering to obtain pretreated gel, cutting the pretreated gel into blocks, washing for 6 days by deionized water, changing the deionized water once every 12h, vacuum-drying the washed gel blocks for 5h at room temperature, obtaining gelatin microspheres, and mixing the graphene oxide and petroleum ether according to a mass ratio of 1: 200, mixing the mixture in a beaker, performing ultrasonic dispersion for 40min under the condition of 65kHz, adding paraffin dispersion liquid with the mass 10 times that of graphene oxide into the beaker, stirring and reacting for 80min under the conditions of 70 ℃ and 400r/min, performing rotary evaporation and concentration for 3h under the conditions of 80 ℃ and 600kPa on the materials in the beaker to obtain a concentrate, performing vacuum drying for 3h under the condition of 60 ℃ on the concentrate to obtain a modified graphene oxide blank, and mixing the modified graphene oxide blank with 30% nitric acid according to the mass ratio of 1: 12, mixing, standing for 40min at room temperature, and filtering to obtain modified graphene oxide; mixing a polyvinyl alcohol aqueous solution with the mass fraction of 7% and a graphene oxide solution with the mass fraction of 3% according to the volume ratio of 8: 1, mixing, stirring and mixing for 2 hours at the temperature of 55 ℃ and the rotating speed of 400r/min under the conditions of 90 ℃ and 400r/min, carrying out electrostatic spinning to obtain pretreated modified polyvinyl alcohol fibers, and carrying out vacuum drying on the pretreated modified polyvinyl alcohol fibers at the temperature of 55 ℃ for 12 hours to obtain the modified polyvinyl alcohol fibers; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300, mixing the mixture in a flask, performing ultrasonic dispersion for 40min under the condition of 55kHz, adjusting the pH of the material in the flask to 10 by using a potassium hydroxide solution with the mass fraction of 20%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min of rotation speed, adjusting the pH of the material in the flask to be neutral by using hydrochloric acid with the mass fraction of 18%, performing suction filtration and water washing to obtain a pre-modified carbon nanotube blank, and performing vacuum drying on the pre-modified carbon nanotube blank for 5h under the condition of 75 ℃ to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 280, mixing the mixture in a conical flask, performing ultrasonic dispersion for 70min under the condition of 60kHz, adding a mixture of ammonia water with the mass fraction of 28% and tetraethoxysilane with the mass fraction of 30% of the mass of the pre-modified carbon nano tube into the conical flask, performing ultrasonic dispersion for 60min under the condition of 60kHz, stirring and reacting for 20h under the conditions of 40 ℃ and 350r/min to obtain a modified carbon nano tube mixture, stirring and mixing the modified carbon nano tube mixture for 20min under the conditions of 40 ℃ and 400r/min, performing suction filtration and drying to obtain a modified carbon nano tube blank, and mixing the modified carbon nano tube blank with hydrochloric acid with the mass fraction of 18% according to the mass ratio of 1: 8, mixing, soaking for 40min at room temperature, and filtering to obtain modified carbon nanotubes; mixing gelatin microspheres with a boric acid solution with the mass fraction of 30% according to the mass ratio of 1: 10, regulating the pH value of a mixture of the gelatin microspheres and a boric acid solution to 2.5 by using hydrochloric acid with the mass fraction of 20%, stirring and mixing for 2 hours at the temperature of 50 ℃ and the rotating speed of 400r/min, regulating the pH value of the mixture of the gelatin microspheres and the boric acid solution to 5.8 by using ammonia water with the mass fraction of 18%, and filtering to obtain an additive, wherein the following components are weighed in sequence in parts by weight: 100 parts of water glass, 20 parts of sodium fluosilicate, 18 parts of mica, 15 parts of modified graphene oxide, 15 parts of modified polyvinyl alcohol fiber, 12 parts of modified carbon nano tube and 8 parts of additive, mixing the water glass and the sodium fluosilicate in a stirrer, adding the mica, the modified graphene oxide, the modified polyvinyl alcohol fiber, the modified carbon nano tube and the additive into the stirrer, and stirring and mixing for 40min under the conditions that the temperature is 50 ℃ and the rotating speed is 400r/min to obtain the anti-cracking inorganic hole sealing agent. The paraffin dispersion liquid is prepared by mixing paraffin with 32 carbon atoms and petroleum ether according to the mass ratio of 1: 12, and obtaining the paraffin dispersion liquid under the electrostatic spinning condition that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning liquid is 0.3 mL/h. The ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 20 to obtain an ethyl orthosilicate mixture. The modulus of the water glass is 2.8.
Comparative example: an anti-cracking inorganic hole sealing agent produced by Shanghai certain scientific and technical material production Limited company.
The anti-cracking inorganic hole sealing agents obtained in examples 1 to 5 and comparative products are subjected to performance detection, and the specific detection method is as follows:
curing the sample coated with the test piece, placing the sample in a thermostat at 200 ℃ for constant temperature treatment for 7 days, and detecting the tensile strength and the elastic modulus of the anti-cracking inorganic hole sealing agent; after drying for 180 days, the presence of cracks was observed.
Specific detection results are shown in table 1:
table 1 anti-cracking inorganic hole sealing agent performance test results
As can be seen from the detection results in Table 1, the anti-cracking inorganic hole sealing agent prepared by the technical scheme of the invention has excellent toughness
Has wide prospect in the development of material corrosion and protection technology industry.
Claims (8)
1. The anti-cracking inorganic hole sealing agent is characterized by comprising the following raw materials in parts by weight: 70-100 parts of water glass, 15-20 parts of sodium fluosilicate and 10-18 parts of mica, wherein the anti-cracking inorganic hole sealing agent further comprises: 10-15 parts of modified graphene oxide, 10-15 parts of modified polyvinyl alcohol fibers, 8-12 parts of modified carbon nanotubes and 5-8 parts of additives;
the preparation method of the modified graphene oxide comprises the following steps:
mixing graphene oxide and petroleum ether according to a mass ratio of 1: 150-1: 200, adding paraffin dispersion liquid with the mass 5-10 times that of graphene oxide after ultrasonic dispersion, stirring and reacting, performing rotary evaporation and concentration, and performing vacuum drying to obtain a modified graphene oxide blank, wherein the modified graphene oxide blank and nitric acid are mixed according to a mass ratio of 1: 8-1: 12, mixing and filtering to obtain modified graphene oxide;
the preparation method of the modified polyvinyl alcohol fiber comprises the following steps:
mixing a polyvinyl alcohol solution and a graphene oxide solution according to a volume ratio of 5: 1-8: 1, mixing, stirring and mixing, performing electrostatic spinning, and drying to obtain modified polyvinyl alcohol fibers;
the preparation method of the modified carbon nano tube comprises the following steps:
mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 280-1: 300, mixing, performing ultrasonic dispersion, adjusting the pH value to 8-10, stirring for reaction, adjusting the pH value to be neutral, performing suction filtration and washing, and performing vacuum drying to obtain a pre-modified carbon nano tube; mixing the pre-modified carbon nano tube with an ethanol solution according to the mass ratio of 1: 200-1: 280, mixing, performing ultrasonic dispersion, adding ammonia water which is 5-8 times of the mass of the pre-modified carbon nano tube and an ethyl orthosilicate mixture which is 10-30 times of the mass of the pre-modified carbon nano tube, performing ultrasonic dispersion, stirring for reaction to obtain a modified carbon nano tube mixture, and mixing the modified carbon nano tube mixture and a silane coupling agent mixture according to a mass ratio of 20: 1-40: 1, mixing, filtering, drying to obtain a modified carbon nanotube blank, and mixing the modified carbon nanotube blank with hydrochloric acid according to a mass ratio of 1: 5-1: 8, mixing and filtering to obtain modified carbon nanotubes;
the preparation method of the additive comprises the following steps:
mixing gelatin microspheres and boric acid solution according to the mass ratio of 1: 6-1: 10, adjusting the pH value to 2.3-2.5, stirring and mixing, adjusting the pH value to 4.8-5.8, and filtering to obtain the additive.
2. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the paraffin dispersion liquid is prepared by mixing paraffin with 24-32 carbon atoms and petroleum ether according to a mass ratio of 1: 10-1: 12 to obtain the paraffin dispersion liquid.
3. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the electrostatic spinning conditions are that a receiving screen covered with aluminum foil paper is used as a receiving device, the receiving distance is 10cm, the spinning voltage is 12kV, and the extrusion rate of the spinning solution is 0.3 mL/h.
4. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the ethanol solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol solution.
5. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and ethanol according to a mass ratio of 1: 15-1: 20 to obtain an ethyl orthosilicate mixture.
6. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the silane coupling agent mixture is prepared by mixing ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-560 with the mass of 0.4-0.6 time that of ethanol, and stirring and mixing to obtain a silane coupling agent mixture.
7. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the gelatin microspheres are sequentially weighed according to parts by weight: 100-120 parts of polyvinyl alcohol, 60-80 parts of gelatin, 300-450 parts of water, 30-50 parts of glutaraldehyde aqueous solution and 10-30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, and vacuum drying to obtain the gelatin microspheres.
8. The crack-resistant inorganic sealant as claimed in claim 1, wherein: the modulus of the water glass is 2.6-2.8.
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