WO2022148465A1 - 气凝胶涂料及其制备方法和气凝胶涂层及其制备方法 - Google Patents

气凝胶涂料及其制备方法和气凝胶涂层及其制备方法 Download PDF

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WO2022148465A1
WO2022148465A1 PCT/CN2022/071071 CN2022071071W WO2022148465A1 WO 2022148465 A1 WO2022148465 A1 WO 2022148465A1 CN 2022071071 W CN2022071071 W CN 2022071071W WO 2022148465 A1 WO2022148465 A1 WO 2022148465A1
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Prior art keywords
aerogel
powder
preparation
aerogel coating
prepare
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PCT/CN2022/071071
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English (en)
French (fr)
Inventor
赵园
魏欢饴
仇若翔
曾献
邹青
段承杰
林继铭
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China General Nuclear Power Corp
China Nuclear Power Technology Research Institute Co Ltd
CGN Power Co Ltd
Lingdong Nuclear Power Co Ltd
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China General Nuclear Power Corp
China Nuclear Power Technology Research Institute Co Ltd
CGN Power Co Ltd
Lingdong Nuclear Power Co Ltd
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Application filed by China General Nuclear Power Corp, China Nuclear Power Technology Research Institute Co Ltd, CGN Power Co Ltd, Lingdong Nuclear Power Co Ltd filed Critical China General Nuclear Power Corp
Priority to EP22736626.7A priority Critical patent/EP4276152A4/en
Publication of WO2022148465A1 publication Critical patent/WO2022148465A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/155—Preparation of hydroorganogels or organogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the invention relates to the field of aerogel coatings, in particular to an aerogel coating and a preparation method thereof, and an aerogel coating and a preparation method thereof.
  • a method for preparing a silica aerogel coating by stirring and grinding using gel powder, organic adhesive, curing agent and film-forming aid as raw materials It is characterized in that the selected formula makes the coating and the base material bond well, can effectively heat insulation, reduce explosion deformation, and has a protective function, and meanwhile, the preparation process is simple and the cost is low.
  • the main components of the aerogel adhesive used in this method are organic components such as water-based polyurethane, which have the defects of poor heat resistance and aging resistance. When the temperature is too high, the adhesive will be thermally decomposed and lose its adhesive properties. Cause the adhesive to fall off, and the long-term use may cause the thermal insulation performance to decline.
  • Another traditional technology discloses a preparation method, which uses a composition composed of epoxy modified resin, phenolic modified resin, silicone modified resin and silicone rubber as the coating matrix, and uses aerogel particles as the coating matrix.
  • Functional filler with polyvinyl alcohol as auxiliary agent to make aerogel coating.
  • the aerogel paint prepared by the method has good dispersibility, good stability, and good high temperature resistance and heat insulation performance.
  • the coating substrate used in this method also has the problem of limited adhesion performance and long-term temperature resistance, and is prone to fall off when used for a long time or subjected to a large external force impact, and is not suitable for long-term use at higher temperatures.
  • aerogel coatings with inorganic binders instead of organic binders are gradually appearing, for example, a technology discloses a method that uses silica-alumina clay and/or industrial solid waste, high-calcium pulverized coal Ash is the main raw material, phosphoric acid and organic tribasic acid are used as compound activators, and hydrogen peroxide and foam stabilizer are used as foaming agents to prepare porous geopolymer composite insulation board.
  • SiO 2 aerogel/porous geopolymer composite insulation board was prepared by in-situ immersion and hydrophobic agent modification.
  • the composite thermal insulation board prepared by the method is light in weight, good in thermal insulation effect, high in compressive strength, high in refractoriness and good in water resistance, and at the same time, the preparation method has low energy consumption and low manufacturing cost, which is favorable for industrial application.
  • the composite insulation board prepared by this method has the problems that the contact between the aerogel and the porous geopolymer composite insulation board is limited, the small amount of aerogel doping leads to the limited thermal insulation effect, and the plate material does not have adhesion and coating. It is difficult to be used in the bonding and heat preservation of some irregular surfaces and tanks.
  • a preparation method of aerogel coating comprising the steps:
  • the aerogel powder is mixed with the geopolymer slurry to prepare an aerogel coating.
  • the aerogel powder and the geopolymer slurry are mixed by means of mechanical stirring or peristaltic stirring .
  • the time of the mechanical stirring or peristaltic stirring is 1 min to 20 min.
  • the method before the step of mixing the aerogel powder and the geopolymer slurry by means of mechanical stirring or peristaltic stirring, the method further comprises directly adding or spraying to mix the aerogel powder The step of adding glue powder to the geopolymer slurry.
  • the volume ratio of the geopolymer slurry to the aerogel powder is 1:(1-5).
  • the aerogel powder is silica aerogel powder.
  • a preparation step of the aerogel powder is also included, and the preparation step of the aerogel powder includes:
  • the aerogel mass is pulverized to prepare the aerogel powder.
  • the method before the step of pulverizing the aerogel block, the method further includes: heat-treating the aerogel block at 400° C. ⁇ 700° C. for 0.5 h ⁇ 5 h.
  • the step of preparing silicon gel by mixing silicon source, water and alcohol solvent includes:
  • the pH of the sol is adjusted to be 8-10 to prepare the silica gel.
  • the step of mixing and stirring the sol and silicon carbide powder is further included.
  • the molar ratio of the silicon carbide powder to the silicon source is (1-10):100.
  • the aging time is 24h-72h; and/or, in the drying step, a method of carbon dioxide supercritical drying is adopted, and the temperature of the carbon dioxide supercritical drying is 32° C. ⁇ 50° C. °C, the pressure is 7.4MPa ⁇ 18MPa.
  • An aerogel coating is prepared by the above-mentioned preparation method of aerogel coating.
  • a preparation method of aerogel coating comprising the steps:
  • the aerogel coating is coated on a substrate, and then cured, so that the aerogel coating is attached to the substrate to prepare an aerogel coating.
  • the curing step includes: curing at 40°C ⁇ 100°C for 4h ⁇ 24h; or, the curing step includes: curing at 17°C ⁇ 23°C and humidity ⁇ 90% Carry out standard curing for 1 day to 28 days.
  • An aerogel coating is prepared by the above-mentioned preparation method of the aerogel coating.
  • the preparation method of the above-mentioned aerogel coating firstly mixes slag powder, fly ash, water glass and water in a certain proportion to prepare a geopolymer slurry, and then mixes the geopolymer slurry with aerogel powder to prepare aerogel powder. glue coating.
  • the geopolymer slurry has the characteristics of high compressive strength (30MPa to 100MPa), high temperature resistance (not less than 800°C), and strong adhesiveness (2 to 3 times that of ordinary cement), so that the preparation
  • the aerogel coating has good high temperature resistance, aging resistance and strong adhesion.
  • aerogel powder As an insulating matrix, aerogel powder has low density, high porosity, and many interfaces, which limit the molecular mean free path and have low solid-state thermal conductivity; at the same time, its porous network structure is mostly Mesopores, the pore size is smaller than the mean free path of gas molecules, which is conducive to suppressing gaseous heat conduction. Therefore, the thermal conductivity at room temperature is lower than that of traditional thermal insulation materials, which can achieve efficient thermal insulation. Therefore, the preparation method of the above-mentioned aerogel paint mixes the geopolymer slurry with the aerogel powder to prepare the aerogel paint, which can make the prepared aerogel paint have good adhesion, high temperature resistance and heat preservation.
  • FIG. 1 is a process flow diagram of a method for preparing an aerogel coating according to an embodiment.
  • the preparation method of the aerogel coating of one embodiment comprises the following steps:
  • Step S110 Mix and stir slag powder, fly ash, water glass and water to prepare a geopolymer slurry.
  • the steps of mixing and stirring slag powder, fly ash, water glass and water include: firstly mixing slag powder, fly ash and water glass with a mass ratio of 4:(0.2-4):(0.5-2) to prepare Dry powder, then mix dry powder with water, the mass ratio of dry powder to water is 1:(0.2 ⁇ 0.5).
  • the above-mentioned geopolymer slurry has the advantages of high compressive strength (30MPa ⁇ 100MPa), high temperature resistance (not lower than 800°C), and strong adhesiveness (2 times to 3 times that of ordinary cement adhesiveness).
  • Traditional aerogel coatings with organic components and even inorganic components such as cement as binders, the above-mentioned geopolymer slurries have the characteristics of high mechanical properties, high temperature resistance, aging resistance and strong adhesion. Gel coatings can effectively solve the problems that conventional aerogel materials cannot be heated for a long time and are easy to age and fall off.
  • Step S120 Mix the aerogel powder with the geopolymer slurry to prepare the aerogel paint.
  • the aerogel powder is mixed with the geopolymer slurry by means of mechanical stirring or peristaltic stirring. Further, the peristaltic stirring is performed using a peristaltic mortar machine.
  • the process parameters in the peristaltic stirring process can be parameters commonly used in the art, and details are not repeated here.
  • the volume ratio of the geopolymer slurry to the aerogel powder is 1:(1-5). In one embodiment, the volume ratio of geopolymer slurry to aerogel powder is 1:1, 1:2, 1:3, 1:4, or 1:5. It can be understood that the volume of the aerogel powder can be measured with a measuring cylinder.
  • the time for mechanical stirring or peristaltic stirring is 1 min to 20 min. In one embodiment, the time of mechanical stirring or peristaltic stirring is 1 min, 5 min, 10 min, 15 min or 20 min.
  • the step of mixing the aerogel powder with the geopolymer slurry by means of mechanical stirring or peristaltic stirring it further comprises adding the aerogel powder into the geopolymer slurry by directly adding or spraying step.
  • the aerogel powder is added into the geopolymer slurry and mixed and stirred, so that the geopolymer slurry and the aerogel powder are fully mixed evenly, which solves the problems of small proportion of aerogel components and uneven distribution, and makes the gas The thermal insulation performance of the gel coat is good.
  • aerogel powders have low density, high porosity, and many interfaces, which limit the molecular mean free path and have low solid-state thermal conductivity; at the same time, their porous network structure is mostly mesoporous, with pore size The size is smaller than the mean free path of gas molecules, which is conducive to suppressing gaseous heat conduction. Therefore, the thermal conductivity at room temperature is lower than that of traditional thermal insulation materials, which can achieve efficient thermal insulation.
  • the aerogel powder is a silica aerogel powder.
  • Al, Si, O and other elements in the geopolymer slurry can form a stable three-dimensional structure with the Si and O components in the silica aerogel, so that the prepared aerogel coating material has good high temperature resistance. , aging resistance and very good mechanical properties, which solves the problem of poor mechanical properties of conventional aerogel coating materials.
  • a preparation step of aerogel powder is also included, and the preparation step of aerogel powder specifically includes:
  • a silicon source, water and an alcohol solvent are mixed to prepare a silicon gel, which is then aged and dried to prepare an aerogel block;
  • the aerogel block is pulverized to prepare an aerogel powder.
  • the silicon source, water and alcohol solvent are mixed, and the steps of preparing the silicon gel include:
  • the silicon source, the alcohol solvent and the water are mixed in a molar ratio of 1:(10-20):(3-15), and then the pH is adjusted to 2-4 to prepare a sol; and
  • the pH of the sol was adjusted to 8-10 to prepare a silica gel.
  • the step of mixing and stirring the sol and the silicon carbide powder is also included. Adding opacifier silicon carbide powder to the aerogel matrix can effectively reduce the radiation heat transfer in a high temperature environment, so that the material still has high thermal insulation performance in a high temperature environment.
  • the molar ratio of the silicon carbide powder to the silicon source is (1-10):100.
  • the molar ratio of silicon carbide powder to silicon source is 1:100, 2:100, 5:100, 8:100 or 10:100.
  • the silicon source is ethyl orthosilicate, methyl orthosilicate or butyl orthosilicate.
  • the silicon source is ethyl orthosilicate.
  • the alcohol solvent is ethanol, methanol or propanol.
  • the alcoholic solvent is ethanol.
  • an acidic reagent is added to adjust the pH.
  • the acidic reagent is hydrochloric acid, nitric acid, and the like.
  • the acidic reagent is hydrochloric acid.
  • an alkaline reagent is added to adjust the pH.
  • the alkaline reagent is ammonia water, sodium hydroxide, potassium hydroxide and the like.
  • the acidic reagent is ammonia water.
  • the aging time is 24h-72h.
  • the carbon dioxide supercritical drying method is adopted, and the temperature of the carbon dioxide supercritical drying is 32° C. to 50° C. and the pressure is 7.4 MPa to 18 MPa.
  • the carbon dioxide supercritical drying method saves the period of surface modification of the material, and reduces the collapse of the internal pore size of the material during the drying process, so that the material has better thermal insulation and mechanical properties.
  • the method further includes: heat-treating the aerogel block at 400° C. to 700° C. for 0.5 h to 5 h.
  • the temperature of the heat treatment is 400°C, 500°C, 600°C or 700°C.
  • the step of heat treatment is performed in a tube furnace.
  • the aerogel block is heat treated to enhance the stability of the skeleton structure of the aerogel material, so that it is less likely to suffer from the problem of thermal insulation performance degradation caused by structural damage at higher temperatures, so that the aerogel powder has better performance. High temperature resistance and thermal insulation properties.
  • the aerogel powder can be directly purchased, or the aerogel block can be directly purchased and obtained after heat treatment and ball milling.
  • the preparation method of the above-mentioned aerogel coating firstly mixes slag powder, fly ash, water glass and water in a certain proportion to prepare a geopolymer slurry, and the geopolymer slurry has a high compressive strength (30MPa ⁇ 100MPa), high temperature resistance (not less than 800°C), strong adhesion (2 to 3 times that of ordinary cement), and at the same time, elements such as Al, Si, O and other elements in the geopolymer slurry can It forms a stable three-dimensional structure with the Si and O components in the silica aerogel, so that the prepared aerogel coating has good high temperature resistance and aging resistance, which can effectively solve the problem that conventional aerogel materials cannot be heated for a long time, The problem of easy aging and shedding.
  • aerogel powder with the geopolymer slurry solves the problems of less proportion of aerogel components and uneven distribution, and makes the thermal insulation material lighter and more thermally insulated. Moreover, the peristaltic stirring or mechanical stirring will not destroy the internal pore structure of the aerogel powder, thereby greatly improving the thermal insulation of the aerogel coating.
  • aerogel has low density, high porosity, and many interfaces, which limit the molecular mean free path and have low solid-state thermal conductivity; at the same time, its porous network structure is more It is mesoporous, and the pore size is smaller than the mean free path of gas molecules, which is conducive to inhibiting gaseous heat conduction. Therefore, the thermal conductivity at room temperature is lower than that of traditional thermal insulation materials, which can achieve efficient thermal insulation. Therefore, the preparation method of the above-mentioned aerogel coating can make the prepared aerogel coating have good adhesion, high temperature resistance and heat preservation.
  • the above-mentioned preparation method of aerogel coating enables the material to be easily coated on the surface of various irregularly shaped materials through the design of the aerogel coating, and through the strength of the material Adhesive properties, closely combined with the interface, greatly expands the application range of the material, reduces the difficulty of implementation, and has a wider range of use, especially for the insulation of space-constrained, weight-constrained and irregular pipeline equipment.
  • Silicon carbide powder is added as a sunscreen in the preparation process of the above-mentioned aerogel coating, and the addition amount and compounding method of the sunscreen are optimized at the same time, which can effectively reduce the radiation heat transfer and solve the problem caused by heat generated at a higher temperature.
  • the heat transfer problem caused by radiation conduction effectively improves the thermal insulation performance of the material at higher temperatures.
  • the stability of the skeleton structure of the aerogel material is enhanced by heat treatment of the aerogel block, so that the thermal insulation performance caused by the structural damage is not easy to occur at a higher temperature. Therefore, the aerogel powder has better high temperature resistance and thermal insulation performance.
  • the preparation method of the above-mentioned aerogel material makes the aerogel material and the geopolymer material evenly mixed by adjusting the water-binder ratio, improving the mixing method, etc., and the geopolymer molecule and the aerogel component form a stable three-dimensional structure, so that the material can be The uniformity and mechanical properties are further optimized.
  • the slag-based polymer is used as a binder in the preparation method of the aerogel coating, the raw materials are simple and easy to obtain, the economy is good, and it has the characteristics of low cost and high performance.
  • the aerogel paint of one embodiment is prepared by the above-mentioned preparation method of the aerogel paint.
  • the aerogel coating has strong adhesion, good high temperature resistance and good thermal insulation performance.
  • the aerogel coating can be easily coated on the surface of various irregular shaped materials, and through the strong Adhesive properties, closely combined with the interface, greatly expands the application range of the material, reduces the difficulty of implementation, and has a wider range of use, especially for the insulation of space-constrained, weight-constrained and irregular pipeline equipment.
  • the aerogel coating is coated on the substrate and then cured to make the aerogel coating adhere to the substrate to prepare the aerogel coating.
  • the aerogel paint is the aerogel paint of the above-mentioned embodiments.
  • the curing step includes: curing at 40°C-100°C for 4h-24h; or, the curing step includes: performing standard curing for 1-28 days under the conditions of 17°C-23°C and humidity ⁇ 90% .
  • the coating method of the aerogel coating is simple and easy to implement, and the aerogel coating can be firmly coated on the surfaces of various regular or irregular shaped substrates by the coating method.
  • the aerogel coating of an embodiment is prepared by the preparation method of the aerogel coating of the above-mentioned embodiment.
  • the blast furnace slag is ground into fine slag powder by ball milling and physical screening.
  • the above-mentioned aerogel paint is coated on the surface of the material, and the standard curing system (temperature is 20 ° C, humidity is 90%) is used for curing for 15 days, so that the aerogel paint is firmly adhered to the surface of the coated material, and the aerogel is prepared. glue coating.
  • the blast furnace slag is ground into fine slag powder by ball milling and physical screening. Mix fine slag powder, fly ash, and instant powdered water glass in a dry powder mixer at a mass ratio of 4:1:1 to make dry powder A. Add water to dry powder A (the mass ratio of dry powder A to water is 2:1), stir evenly, and prepare a geopolymer slurry.
  • the preparation process of the aerogel paint of this embodiment is similar to the preparation process of the aerogel paint of Example 2, and the difference is that step (4) is different.
  • the step (4) of this embodiment is as follows: measure the aerogel powder of 3 times the volume of the geopolymer, and stir for 8 minutes by means of a sprayer and peristaltic stirring until the aerogel coating is uniformly stirred.
  • the preparation process of the aerogel coating in this example is the same as the preparation process of the aerogel coating in Example 2.
  • the preparation process of the aerogel paint of this embodiment is similar to the preparation process of the aerogel paint of Example 2, and the difference is that step (4) is different.
  • the step (4) of this embodiment is as follows: measuring the aerogel powder of 4 times the volume of the geopolymer, and stirring for 8 minutes by means of a sprayer and peristaltic stirring until the aerogel coating is uniformly stirred.
  • the preparation process of the aerogel coating in this example is the same as the preparation process of the aerogel coating in Example 2.
  • the preparation process of the aerogel paint in this embodiment is the same as the preparation process of the aerogel paint in Example 2, and will not be repeated here.
  • the preparation process of the aerogel coating in this embodiment is to coat the aerogel coating on the surface of the material, and adopt a standard curing system (temperature of 20° C., humidity of 90%) for 1 day to make the aerogel coating
  • the material is firmly bonded to the surface of the material to be coated, producing an aerogel coating.
  • the preparation process of the aerogel paint in this embodiment is the same as the preparation process of the aerogel paint in Example 2, and will not be repeated here.
  • the preparation process of the aerogel coating in this embodiment is to coat the aerogel coating on the surface of the material, and use steam at 80°C for 4 hours to make the aerogel coating material firmly adhere to the surface of the coated material. Aerogel coating.
  • the preparation process of the aerogel coating in this embodiment is similar to the preparation process of the aerogel coating in Example 1, and the difference is that step (4) is different.
  • the step (4) of the preparation process of the aerogel coating of this embodiment is: adding the aerogel powder directly into the geopolymer slurry, and then mixing the aerogel powder with the geopolymer slurry by mechanical stirring Mix well to prepare aerogel paint.
  • the preparation process of the aerogel coating in this example is the same as the preparation process of the aerogel coating in Example 1.
  • the preparation process of the aerogel paint of Comparative Example 1 is similar to the preparation process of the aerogel paint of Example 1, the difference is that step (3) is different.
  • the step (3) of the preparation process of the aerogel paint of Comparative Example 1 is as follows: using the ball milling method and the method of physical screening, the blast furnace slag is ground into fine slag powder. Mix the fine slag powder, fly ash, and instant powdered water glass in a dry powder mixer at a mass ratio of 4:1:0.2 to make dry powder A. Add water to dry powder A (the mass ratio of dry powder A to water is 8:1), stir evenly, and prepare a geopolymer slurry.
  • the preparation process of the aerogel coating of Comparative Example 1 is the same as the preparation process of the aerogel coating of Example 1.
  • the properties of the prepared aerogel coatings of Examples 1-7 and Comparative Example 1 were tested, and the test results are shown in Table 1 below.
  • the test method is as follows: the high temperature resistance test adopts calcination at 800 °C for not less than 6 hours, and the properties of the material still meet the performance index requirements.
  • the room temperature thermal conductivity of the aerogel coating was tested using the GB/T 10295-2008 test standard.
  • the thermal conductivity of the aerogel coating at 800°C was tested using the YB/T 4130-2005 test standard.
  • the compressive strength of the aerogel coating was tested using the GB/T 1964-1996 test standard.
  • the adhesive strength of the aerogel coating was measured by the TCH-3000 adhesive strength puller test method.
  • the aerogel coatings prepared in Examples 1 to 7 have good high temperature resistance, low thermal conductivity at room temperature and 800 °C, and good thermal insulation performance. High bond strength and compressive strength.
  • the temperature resistance of the aerogel coating of Comparative Example 1 is only 600 ° C, the high temperature resistance is poor, and the bonding strength and compressive strength are far less than the aerogel coatings of Examples 1-7, and the room temperature is hot.
  • the conductivity is higher, and the thermal insulation performance is also lower than that of the aerogel coatings of Examples 1-7.

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Abstract

本发明涉及一种气凝胶涂料及其制备方法和气凝胶涂层及其制备方法。上述气凝胶涂料的制备方法包括如下步骤：先将质量比为4:(0.2～4):(0.5～2)的矿渣粉、粉煤灰和水玻璃进行混合，制备干粉，然后将干粉与水混合，干粉与水的质量比为1:(0.2～0.5)，制备地聚物浆料；以及将气凝胶粉末与地聚物浆料混合，制备气凝胶涂料。上述气凝胶涂料的制备方法能够使制备的气凝胶涂料具有良好的粘结性、耐高温性和保温性。

Description

气凝胶涂料及其制备方法和气凝胶涂层及其制备方法
本申请要求于2021年01月11日提交国家知识产权局、申请号为202110034734.1、发明名称为“气凝胶涂料及其制备方法和气凝胶涂层及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及气凝胶涂料领域，特别是涉及一种气凝胶涂料及其制备方法和气凝胶涂层及其制备方法。
背景技术
传统的气凝胶涂覆材料多采用有机粘结剂组分，具有粘结性好的优点，但存在不能长期受热、易老化脱落的问题，例如传统技术中公开了一种以二氧化硅气凝胶粉、有机胶粘剂、固化剂、成膜助剂为原料，通过搅拌、研磨制备二氧化硅气凝胶涂料的方法。其特点在于所选配方使涂料与基材良好键合，可有效隔热、减少爆炸变形，具有防护功能，同时制备工艺简单，成本低廉。但该方法所用的气凝胶粘接剂主要组分为水性聚氨酯等有机组分，存在耐热和耐老化性能较差的缺陷，在温度过高时粘结剂会受热分解丧失粘接性能从而造成粘接物脱落，长时间使用会有造成保温性能下降的可能。
还有一种传统技术公开了一种制备方法，该方法以自由环氧改性树脂、酚醛改性树脂、有机硅改性树脂和有机硅橡胶组成的组合物作为涂料基体，以气凝胶颗粒为功能填料，以聚乙烯醇等为助剂制成气凝胶涂料。该方法制备的气凝胶涂料分散性好、稳定性好、耐高温及隔热性能好。但该方法所采用的涂料基体同样存在粘接性能和长期耐温性能有限的问题，在长久使用或者经受较大外力冲击时容易发生脱落现象，并且不适用长时间在较高温度下使用。
因此，逐渐出现了以无机粘结剂代替有机粘结剂的气凝胶涂料，例如，一 种技术公开了一种方法，该方法以硅铝质粘土和/或工业固体废物、高钙粉煤灰为主要原料，以磷酸和有机三元酸为复配激发剂制，以双氧水和稳泡剂为发泡剂制备多孔地聚物复合保温板，并在此基础上利用溶胶-凝胶法原位浸渍、憎水剂改性制备SiO 2气凝胶/多孔地聚物复合保温板。该方法制备的复合保温板质量轻、保温效果好、抗压强度大、耐火度高、防水性好，同时制备方法能耗较低、制造成本较低，利于产业化应用。但该方法制备的复合保温板存在气凝胶与多孔地聚物复合保温板接触有限，气凝胶掺杂量小导致其保温效果有限的问题，且板状材料不具有粘接性和涂覆性，难以应用在一些不规则表面与罐体等的粘接保温。
发明内容
基于此，有必要提供一种能够使制备的气凝胶涂料兼具粘接性好、耐高温且保温效果好的气凝胶涂料的制备方法。
此外，还有必要提供一种气凝胶涂料和气凝胶涂层及其制备方法。
一种气凝胶涂料的制备方法，包括如下步骤：
先将质量比为4:(0.2～4):(0.5～2)的矿渣粉、粉煤灰和水玻璃进行混合，制备干粉，然后将所述干粉与水混合，所述干粉与水的质量比为1:(0.2～0.5)，制备地聚物浆料；以及
将气凝胶粉末和所述地聚物浆料混合，制备气凝胶涂料。
在其中一个实施例中，在所述将气凝胶粉末和所述地聚物浆料混合的步骤中，采用机械搅拌或蠕动搅拌的方式将气凝胶粉末和所述地聚物浆料混合。
在其中一个实施例中，所述机械搅拌或蠕动搅拌的时间为1min～20min。
在其中一个实施例中，在所述采用机械搅拌或蠕动搅拌的方式将气凝胶粉末和所述地聚物浆料混合的步骤之前，还包括采用直接添加或者喷雾的方式将所述气凝胶粉末加入到所述地聚物浆料中的步骤。
在其中一个实施例中，所述地聚物浆料与所述气凝胶粉末的体积比为1:(1～5)。
在其中一个实施例中，所述气凝胶粉末为二氧化硅气凝胶粉末。
在其中一个实施例中，还包括气凝胶粉末的制备步骤，所述气凝胶粉末的制备步骤包括：
将硅源、水和醇类溶剂混合，制备硅凝胶，然后进行老化、干燥，制备气凝胶块；以及
将所述气凝胶块进行粉碎，制备所述气凝胶粉末。
在其中一个实施例中，在将所述气凝胶块进行粉碎的步骤之前，还包括：将所述气凝胶块在400℃～700℃下进行热处理0.5h～5h。
在其中一个实施例中，所述将硅源、水和醇类溶剂混合，制备硅凝胶的步骤包括：
将所述硅源、所述醇类溶剂和水按摩尔比为1:(10～20):(3～15)的比例混合，然后调节pH为2～4，制备溶胶；以及
调节所述溶胶的pH为8～10，制备所述硅凝胶。
在其中一个实施例中，在所述调节所述溶胶的pH为8～10的步骤之前，还包括将所述溶胶与碳化硅粉混合搅拌的步骤。
在其中一个实施例中，所述碳化硅粉与所述硅源的摩尔比为(1～10):100。
在其中一个实施例中，所述老化的时间为24h～72h；及/或，在所述干燥的步骤中，采用二氧化碳超临界干燥的方式，所述二氧化碳超临界干燥的温度为32℃～50℃，压力为7.4MPa～18MPa。
一种气凝胶涂料，由上述的气凝胶涂料的制备方法制备得到。
一种气凝胶涂层的制备方法，包括如下步骤：
将上述气凝胶涂料涂覆在基材上，然后进行养护，使所述气凝胶涂料附着在所述基材上，制备气凝胶涂层。
在其中一个实施例中，所述养护的步骤包括：在40℃～100℃蒸汽下养护4h～24h；或者，所述养护的步骤包括：在17℃～23℃、湿度≥90％的条件下进行标准养护1天～28天。
一种气凝胶涂层，由上述的气凝胶涂层的制备方法制备得到。
上述气凝胶涂料的制备方法先将矿渣粉、粉煤灰、水玻璃及水按一定比例混合，制备地聚物浆料，然后将地聚物浆料与气凝胶粉末混合，制备气凝胶涂 料。该地聚物浆料具有高抗压强度(30MPa～100MPa)、耐高温(不低于800℃)、强粘接性(普通水泥粘接性的2倍～3倍)的特点，从而使制备的气凝胶涂料具有良好的耐高温、耐老化性以及强粘结性。另外，气凝胶粉体作为隔热基体，密度较低、孔隙率较高、界面较多，对分子平均自由程具有限制作用，具有较低的固态热导率；同时其多孔网络构多呈介孔，孔径尺寸小于气体分子平均自由程，有利于抑制气态热传导，因此常温下导热系数较传统保温材料更低，可实现高效保温。因此，上述气凝胶涂料的制备方法将地聚物浆料与气凝胶粉末混合制备气凝胶涂料，能够使制备的气凝胶涂料具有良好的粘结性、耐高温性和保温性。
附图说明
图1为一实施方式的气凝胶涂料的制备方法的工艺流程图。
具体实施方式
为了便于理解本发明，下面将结合具体实施方式对本发明进行更全面的描述。具体实施方式中给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体地实施例的目的，不是旨在于限制本发明。
请参阅图1，一实施方式的气凝胶涂料的制备方法，包括如下步骤：
步骤S110：将矿渣粉、粉煤灰、水玻璃及水混合搅拌，制备地聚物浆料。
将矿渣粉、粉煤灰、水玻璃及水混合搅拌的步骤包括：先将质量比为4：(0.2～4)：(0.5～2)的矿渣粉、粉煤灰和水玻璃进行混合，制备干粉，然后将干粉与水混合，干粉与水的质量比为1:(0.2～0.5)。
具体地，在将矿渣粉、粉煤灰和水玻璃进行混合的步骤中，在干粉搅拌机中混合。
在将干粉与水混合的步骤中，在高速搅拌机中搅拌2min～10min，以使地聚物浆料混合均匀，没有大颗粒存在。
上述地聚物浆料具有高抗压强度(30MPa～100MPa)、耐高温(不低于800℃)、强粘接性(普通水泥粘接性的2倍～3倍)的优点，相较于传统以有机组分甚至水泥等无机组分作为粘接剂的气凝胶涂料，上述的地聚物浆料具有高机械性能、耐高温、耐老化和强粘接性等特点，所制备的气凝胶涂料可有效解决常规气凝胶材料不能长期受热、易老化脱落的问题。
步骤S120：将气凝胶粉末与地聚物浆料混合，制备气凝胶涂料。
具体地，采用机械搅拌或蠕动搅拌的方式将气凝胶粉末与地聚物浆料混合。进一步地，采用蠕动式砂浆机进行蠕动搅拌。蠕动搅拌过程中的工艺参数可以为本领域常用的参数，在此不再赘述。
地聚物浆料与气凝胶粉末的体积比为1:(1～5)。在其中一个实施例中，地聚物浆料与气凝胶粉末的体积比为1:1、1:2、1:3、1:4或1:5。可以理解，气凝胶粉末的体积用量筒测量即可。
具体地，采用机械搅拌或者蠕动搅拌的时间为1min～20min。在其中一个实施例中，机械搅拌或蠕动搅拌的时间为1min、5min、10min、15min或20min。
优选地，采用机械搅拌或蠕动搅拌的方式将气凝胶粉末与地聚物浆料混合的步骤之前，还包括采用直接添加或者喷雾的方式将气凝胶粉末加入到地聚物浆料中的步骤。将气凝胶粉末加入到地聚物浆料中并混合搅拌，使地聚物浆料与气凝胶粉末充分混合均匀，解决了气凝胶组分比例少、分布不均匀等问题，使气凝胶涂料的保温性能好。
具体地，气凝胶粉末的密度较低、孔隙率较高、界面较多，对分子平均自由程具有限制作用，具有较低的固态热导率；同时其多孔网络构多呈介孔，孔径尺寸小于气体分子平均自由程，有利于抑制气态热传导，因此常温下导热系数较传统保温材料更低，可实现高效保温。
优选地，气凝胶粉末为二氧化硅气凝胶粉末。地聚物浆料中的Al、Si、O等元素可以与二氧化硅气凝胶中的Si、O组分形成稳定的三维结构，从而使制备的气凝胶涂覆材料在具有良好耐高温、耐老化性能的同时还具有非常好的机 械性能，解决了常规气凝胶涂覆材料机械性能差的问题。
在步骤S120之前，还包括气凝胶粉末的制备步骤，气凝胶粉末的制备步骤具体包括：
将硅源、水和醇类溶剂混合，制备硅凝胶，然后进行老化、干燥，制备气凝胶块；
将气凝胶块进行粉碎，制备气凝胶粉末。
将硅源、水和醇类溶剂混合，制备硅凝胶的步骤包括：
将硅源、醇类溶剂和水按摩尔比为1:(10～20):(3～15)的比例混合，然后调节pH为2～4，制备溶胶；以及
调节溶胶的pH为8～10，制备硅凝胶。
在调节溶胶的pH为8～10的步骤之前，还包括将溶胶与碳化硅粉混合搅拌的步骤。在气凝胶基体中加入遮光剂碳化硅粉，可在高温环境下有效降低辐射传热，使材料在高温环境下仍具有高效保温性能。
优选地，碳化硅粉与硅源的摩尔比为(1～10):100。在其中一个实施例中，碳化硅粉与硅源的摩尔比为1:100、2:100、5:100、8:100或10:100。
具体地，硅源为正硅酸乙酯、正硅酸甲酯或正硅酸丁酯。优选地，硅源为正硅酸乙酯。
醇类溶剂为乙醇、甲醇或丙醇。优选地，醇类溶剂为乙醇。
具体地，在调节pH为2～4的步骤中，加入酸性试剂调剂pH。例如，酸性试剂为盐酸、硝酸等。优选地，酸性试剂为盐酸。
在调剂pH为8～10的步骤中，加入碱性试剂调节pH。例如，碱性试剂为氨水、氢氧化钠、氢氧化钾等。优选地，酸性试剂为氨水。
优选地，老化的时间为24h～72h。
在干燥的步骤中，采用二氧化碳超临界干燥的方式，二氧化碳超临界干燥的温度为32℃～50℃，压力为7.4MPa～18MPa。相较于真空干燥与常压干燥方法，采用二氧化碳超临界干燥方法节省了材料表面改性的周期，并且降低了干燥过程中材料内部孔径的坍塌，使材料具有更好的隔热和机械性能。
具体地，在将气凝胶块进行粉碎的步骤之前，还包括：将气凝胶块在400℃ ～700℃下进行热处理0.5h～5h。在其中一个实施例中，热处理的温度为400℃、500℃、600℃或700℃。具体地，热处理的步骤在管式炉中进行。
将气凝胶块进行热处理，增强气凝胶材料骨架结构的稳定性，从而使其在较高温度下不易发生由结构破坏而导致的保温性能下降问题，使气凝胶粉体有更好的耐高温性能和保温隔热性能。
可以理解，气凝胶粉体可以直接购买得到，或者直接购买气凝胶块，经热处理、球磨后得到。
上述气凝胶涂料的制备方法至少具有以下优点：
(1)上述气凝胶涂料的制备方法先将矿渣粉、粉煤灰、水玻璃及水按一定比例混合，制备地聚物浆料，该地聚物浆料具有高抗压强度(30MPa～100MPa)、耐高温(不低于800℃)、强粘接性(普通水泥粘接性的2倍～3倍)的特点，同时，地聚物浆体中的Al、Si、O等元素可以与二氧化硅气凝胶中的Si、O组分形成稳定的三维结构，从而使制备的气凝胶涂料具有良好的耐高温、耐老化性，可有效解决常规气凝胶材料不能长期受热、易老化脱落的问题。将气凝胶粉末与地聚物浆料混合，解决了气凝胶组分比例少、分布不均匀等问题，使保温材料更轻质、更保温。且蠕动搅拌或机械搅拌不会破坏气凝胶粉末内部孔隙结构，从而大大提高了气凝胶涂料的隔热性。另外，气凝胶作为隔热基体，气凝胶密度较低、孔隙率较高、界面较多，对分子平均自由程具有限制作用，具有较低的固态热导率；同时其多孔网络构多呈介孔，孔径尺寸小于气体分子平均自由程，有利于抑制气态热传导，因此常温下导热系数较传统保温材料更低，可实现高效保温。因此，上述气凝胶涂料的制备方法能够使制备的气凝胶涂料具有良好的粘结性、耐高温性和保温性。
(2)不同于毡、板类保温材料，上述气凝胶涂料的制备方法通过气凝胶涂料的设计，使材料可以方便地涂覆在各类不规则形状的材料表面，并且通过材料的强粘附特性，紧密与界面结合，极大地拓展了材料的使用范围，降低了实施难度，使用范围更广，尤其适用于空间受限、重量受限和不规则管道设备等的保温。
(3)上述气凝胶涂料的制备过程中加入碳化硅粉作为遮光剂，同时对遮光 剂添加量、复合方式进行优化，可有效降低辐射传热，解决了在较高温度下发生的由热辐射传导所导致的热传递问题，有效提升了材料在较高温度下的保温性能。
(4)上述气凝胶涂料的制备过程中通过对气凝胶块进行热处理，增强气凝胶材料骨架结构的稳定性，从而使其在较高温度下不易发生由结构破坏而导致的保温性能下降问题，从而使气凝胶粉体有更好的耐高温性能和保温性能。
(5)地聚物浆料的组分、配比以及与气凝胶粉末的复合方式、复合比例等因素都对最终材料的均匀性和保温性能有较大影响。上述气凝胶材料的制备方法通过调整水胶比、改善混合方式等方法使气凝胶材料与地聚物材料均匀混合，地聚物分子与气凝胶组分形成稳定的三维结构，使得材料均匀性和机械性能进一步优化。
(6)上述气凝胶涂料的制备方法中使用矿渣基地聚物作为粘结剂，原料简便易得、经济性好，具有低成本、高性能的特点。
一实施方式的气凝胶涂料，由上述的气凝胶涂料的制备方法制备得到。该气凝胶涂料的粘结性强、耐高温性好且在保温隔热性能好，此外，该气凝胶涂料可以方便地涂覆在各类不规则形状的材料表面，并且通过材料的强粘附特性，紧密与界面结合，极大地拓展了材料的使用范围，降低了实施难度，使用范围更广，尤其适用于空间受限、重量受限和不规则管道设备等的保温。
一实施方式的气凝胶涂层的制备方法，包括如下步骤：
将气凝胶涂料涂覆在基材上，然后进行养护，使气凝胶涂料附着在基材上，制备气凝胶涂层。具体地，气凝胶涂料为上述实施方式的气凝胶涂料。
具体地，养护的步骤包括：在40℃～100℃蒸汽下养护4h～24h；或者，养护的步骤包括：在17℃～23℃、湿度≥90％的条件下进行标准养护1天～28天。
上述气凝胶涂料的涂覆方法简单易行，且通过上述涂覆方法，使气凝胶涂料牢固地涂覆在各类规则或不规则形状的基材表面。
一实施方式的气凝胶涂层，由上述实施方式的气凝胶涂层制备方法制备得到。
以下为具体实施例部分：
实施例1
本实施例的气凝胶涂料的制备过程具体如下：
(1)将正硅酸乙酯、乙醇均匀混合成溶液A，然后将去离子水逐滴加入到溶液A中(正硅酸乙酯、乙醇与水的摩尔比1:10:5)，加入盐酸调节pH为2，待形成溶胶后加入氨水调节pH为8，制备成硅凝胶，将硅凝胶在乙醇中老化2天后，以超临界CO 2进行干燥(干燥温度为40℃，压力为9MPa)，制备气凝胶块。
(2)将气凝胶块在管式炉中500℃条件下热处理1h，得到耐高温气凝胶块。利用球磨法将耐高温气凝胶块制成气凝胶粉末。
(3)利用球磨法以及物理筛分的方法，将高炉矿渣磨成细矿渣粉体。将细矿渣粉体、粉煤灰与速溶粉状水玻璃按质量比4:1:1的比例在干粉搅拌机中混合均匀，制成干粉A。向干粉A中加入水(干粉A与水的质量比为2:1)，搅拌均匀后制成地聚物浆料。
(4)量取1倍地聚物体积的气凝胶粉末，利用喷雾机加蠕动搅拌的方式搅拌8min至搅拌均匀，得到气凝胶涂料。
本实施例的气凝胶涂层的制备方法具体如下：
将上述气凝胶涂料涂覆于材料表面，采用标准养护制度(温度为20℃，湿度为90％)养护15天，使气凝胶涂料牢固粘接于被涂覆材料的表面，制备气凝胶涂层。
实施例2
本实施例的气凝胶涂料的制备过程具体如下：
(1)将正硅酸乙酯、乙醇均匀混合成溶液A，然后将去离子水逐滴加入到溶液A中(正硅酸乙酯、乙醇、水摩尔比1:10:5)，调节pH为2，待形成溶胶后加入SiC粉末(SiC与正硅酸乙酯的摩尔比为0.06:1)，持续搅拌分散，待形成溶胶后加入氨水调节pH为8，制备硅凝胶。将硅凝胶置于乙醇中老化2天，然后以超临界CO 2进行干燥(干燥温度为40℃，压力为9MPa)，制备气凝胶块。
(2)将气凝胶块在管式炉中500℃条件下热处理1h，得到耐高温气凝胶块。 利用球磨法将气凝胶块制成气凝胶粉末。
(3)利用球磨法以及物理筛分的方法，将高炉矿渣磨细成细矿渣粉体。将细矿渣粉体、粉煤灰、速溶粉状水玻璃按质量比4:1:1比例在干粉搅拌机中混合均匀，制成干粉A。向干粉A中加入水(干粉A与水的质量比为2:1)，搅拌均匀后制成地聚物浆料。
(4)量取2倍地聚物体积的气凝胶粉末，利用喷雾机加蠕动搅拌的方式搅拌8min至搅拌均匀，得到气凝胶涂料。
本实施例的气凝胶涂层的制备方法具体如下：
将气凝胶涂料涂覆于材料表面，采用标准养护制度(温度为20℃，湿度为90％)养护15天，使气凝胶涂料牢固粘接于被涂覆材料的表面，制备气凝胶涂层。
实施例3
本实施例的气凝胶涂料的制备过程与实施例2的气凝胶涂料的制备过程相似，区别在于：步骤(4)不同。该实施例的步骤(4)为：量取3倍地聚物体积的气凝胶粉末，利用喷雾机加蠕动搅拌的方式搅拌8min至搅拌均匀，得到气凝胶涂料。
本实施例的气凝胶涂层的制备过程与实施例2的气凝胶涂层的制备过程相同。
实施例4
本实施例的气凝胶涂料的制备过程与实施例2的气凝胶涂料的制备过程相似，区别在于：步骤(4)不同。该实施例的步骤(4)为：量取4倍地聚物体积的气凝胶粉末，利用喷雾机加蠕动搅拌的方式搅拌8min至搅拌均匀，得到气凝胶涂料。
本实施例的气凝胶涂层的制备过程与实施例2的气凝胶涂层的制备过程相同。
实施例5
本实施例的气凝胶涂料的制备过程与实施例2的气凝胶涂料的制备过程相同，不再赘述。
本实施例的气凝胶涂层的制备过程为将气凝胶涂料涂覆于材料表面，采用采用标准养护制度(温度为20℃，湿度为90％)养护1天，使气凝胶涂覆材料牢固粘接于被涂覆材料的表面，制备气凝胶涂层。
实施例6
本实施例的气凝胶涂料的制备过程与实施例2的气凝胶涂料的制备过程相同，不再赘述。本实施例的气凝胶涂层的制备过程为将气凝胶涂料涂覆于材料表面，采用80℃蒸汽养护4h，使气凝胶涂覆材料牢固粘接于被涂覆材料的表面，制备气凝胶涂层。
实施例7
本实施例的气凝胶涂料的制备过程与实施例1的气凝胶涂料的制备过程相似，区别在于：步骤(4)不同。本实施例的气凝胶涂料的制备过程的步骤(4)为：将气凝胶粉末直接加入到地聚物浆料中，然后通过机械搅拌的方式使气凝胶粉末与地聚物浆料混合均匀，制备气凝胶涂料。
本实施例的气凝胶涂层的制备过程与实施例1的气凝胶涂层的制备过程相同。
对比例1
对比例1的气凝胶涂料的制备过程与实施例1的气凝胶涂料的制备过程相似，区别在于：步骤(3)不同。对比例1的气凝胶涂料的制备过程的步骤(3)为：利用球磨法以及物理筛分的方法，将高炉矿渣磨细成细矿渣粉体。将细矿渣粉体、粉煤灰、速溶粉状水玻璃按质量比4:1:0.2比例在干粉搅拌机中混合均匀，制成干粉A。向干粉A中加入水(干粉A与水的质量比为8:1)，搅拌均匀后制成地聚物浆料。
对比例1的气凝胶涂层的制备过程与实施例1的气凝胶涂层的制备过程相同。
对上述实施例1-7和对比例1的制备的气凝胶涂层的性能进行测试，测试结果如下表1所示。测试方法如下：耐高温测试采用在800℃煅烧不少于6h后，材料各项性能仍然满足性能指标要求。采用GB/T 10295-2008测试标准对气凝胶涂层的常温导热率进行测试。采用YB/T 4130-2005测试标准对气凝胶涂层的 800℃热导率进行测试。采用GB/T 1964-1996测试标准对气凝胶涂层的压缩强度进行测试。采用TCH-3000粘结强度拉拔仪试验方法对气凝胶涂层的粘接强度进行测定。
表1气凝胶涂层的性能测试结果
Figure PCTCN2022071071-appb-000001
从上述表1中可以看出，实施例1～实施例7所制备的气凝胶涂层的耐高温性好，且在常温和800℃下的热导率均较低，保温性能较好，粘结强度和抗压强度高。而对比例1的气凝胶涂层的耐温性仅为600℃，耐高温性较差，粘结强度和抗压强度也远不如实施例1-7的气凝胶涂层，且常温热导率较高，保温性能较实施例1-7的气凝胶涂层也有所下降。另外，由实施例2～4的比较中可以看出，在其他条件不变的情况下，气凝胶粉末的用量增加，气凝胶涂料的粘结强度和抗压强度稍有下降，同时保温性能有较多提升。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改 进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (16)

  1. 一种气凝胶涂料的制备方法，其特征在于，包括如下步骤：
    先将质量比为4:(0.2～4):(0.5～2)的矿渣粉、粉煤灰和水玻璃进行混合，制备干粉，然后将所述干粉与水混合，所述干粉与水的质量比为1:(0.2～0.5)，制备地聚物浆料；及
    将气凝胶粉末和所述地聚物浆料混合，制备气凝胶涂料。
  2. 根据权利要求1所述的气凝胶涂料的制备方法，其特征在于，在所述将气凝胶粉末和所述地聚物浆料混合的步骤中，采用机械搅拌或蠕动搅拌的方式将气凝胶粉末和所述地聚物浆料混合。
  3. 根据权利要求2所述的气凝胶涂料的制备方法，其特征在于，所述机械搅拌或者蠕动搅拌的时间为1min～20min。
  4. 根据权利要求2所述的气凝胶涂料的制备方法，其特征在于，在所述采用机械搅拌或者蠕动搅拌的方式将气凝胶粉末和所述地聚物浆料混合的步骤之前，还包括采用直接添加或喷雾的方式将所述气凝胶粉末加入到所述地聚物浆料中的步骤。
  5. 根据权利要求1所述的气凝胶涂料的制备方法，其特征在于，所述地聚物浆料与所述气凝胶粉末的体积比为1:(1～5)。
  6. 根据权利要求1～5任一项所述的气凝胶涂料的制备方法，其特征在于，所述气凝胶粉末为二氧化硅气凝胶粉末。
  7. 根据权利要求1～5任一项所述的气凝胶涂料的制备方法，其特征在于，还包括气凝胶粉末的制备步骤，所述气凝胶粉末的制备步骤包括：
    将硅源、水和醇类溶剂混合，制备硅凝胶，然后进行老化、干燥，制备气凝胶块；以及
    将所述气凝胶块进行粉碎，制备所述气凝胶粉末。
  8. 根据权利要求7所述的气凝胶涂料的制备方法，其特征在于，在所述将所述气凝胶块进行粉碎的步骤之前，还包括：将所述气凝胶块在400℃～700℃下进行热处理0.5h～5h。
  9. 根据权利要求7所述的气凝胶涂料的制备方法，其特征在于，所述将硅源、水和醇类溶剂混合，制备硅凝胶的步骤包括：
    将所述硅源、所述醇类溶剂和水按摩尔比为1:(10～20):(3～15)的比例混合，然后调节pH为2～4，制备溶胶；以及
    调节所述溶胶的pH为8～10，制备所述硅凝胶。
  10. 根据权利要求9所述的气凝胶涂料的制备方法，其特征在于，在所述调节所述溶胶的pH为8～10的步骤之前，还包括将所述溶胶与碳化硅粉混合搅拌的步骤。
  11. 根据权利要求10所述的气凝胶涂料的制备方法，其特征在于，所述碳化硅粉与所述硅源的摩尔比为(1～10):100。
  12. 根据权利要求7所述的气凝胶涂料的制备方法，其特征在于，所述老化的时间为24h～72h；及/或，
    在所述干燥的步骤中，采用二氧化碳超临界干燥的方式，所述二氧化碳超临界干燥的温度为32℃～50℃，压力为7.4MPa～18MPa。
  13. 一种气凝胶涂料，其特征在于，由权利要求1～12任一项所述的气凝胶涂料的制备方法制备得到。
  14. 一种气凝胶涂层的制备方法，其特征在于，包括如下步骤：
    将权利要求13所述的气凝胶涂料涂覆在基材上，然后进行养护，使所述气凝胶涂料附着在所述基材上，制备气凝胶涂层。
  15. 根据权利要求14所述的气凝胶涂层的制备方法，其特征在于，所述养护的步骤包括：在40℃～100℃蒸汽下养护4h～24h；或者，所述养护的步骤包括：在17℃～23℃、湿度≥90％的条件下进行标准养护1天～28天。
  16. 一种气凝胶涂层，其特征在于，由权利要求14或15所述的气凝胶涂层的制备方法制备得到。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115637061A (zh) * 2022-10-11 2023-01-24 航天特种材料及工艺技术研究所 一种高性能隔热涂层用隔热填料的制备方法
CN115849863A (zh) * 2022-11-23 2023-03-28 江苏朗耐德耐火材料有限公司 一种耐火型气凝胶复合保温材料及其制备方法
CN118164720A (zh) * 2024-03-12 2024-06-11 湖南工程学院 一种气凝胶-玻化微珠保温砂浆及其制备方法
CN118666558A (zh) * 2024-07-09 2024-09-20 河南兴安新型建筑材料有限公司 一种柔性气凝胶保温砌块及其制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112852196B (zh) * 2021-01-11 2022-05-10 中广核研究院有限公司 气凝胶涂料及其制备方法和气凝胶涂层及其制备方法
CN114806240A (zh) * 2022-05-30 2022-07-29 中广核研究院有限公司 保温隔热涂料及其制备方法与应用
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CN121064661B (zh) * 2025-11-06 2026-02-24 华南理工大学 一种地聚物基气凝胶防火涂料及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130010575A (ko) * 2011-07-19 2013-01-29 안영화 에너지 절감 및 건강기능을 위한 건축용 판재 조성물, 그의 제조방법 및 이에 따라 제조된 판재
CN104302597A (zh) * 2012-03-30 2015-01-21 陶氏环球技术有限责任公司 地聚合物前体-气凝胶组合物
US20150102540A1 (en) * 2012-05-09 2015-04-16 Shawcor Ltd. Thermal Insulating Concrete Composition
CN104725958A (zh) * 2015-03-23 2015-06-24 苏州市神龙门窗有限公司 一种户外门窗的隔热涂料及其制备方法
CN107117625A (zh) * 2017-06-19 2017-09-01 浙江省普瑞科技有限公司 一种高透光率二氧化硅气凝胶的制备方法
CN110563438A (zh) * 2019-10-10 2019-12-13 湖北三江航天红阳机电有限公司 一种疏水铝硅气凝胶隔热材料的制备方法
CN112852196A (zh) * 2021-01-11 2021-05-28 中广核研究院有限公司 气凝胶涂料及其制备方法和气凝胶涂层及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2011148097A (ru) * 2009-04-27 2013-06-10 Роквул Интернэшнл А/С Аэрогелевые композиции и способы их изготовления и использования
GB201309061D0 (en) * 2013-05-17 2013-07-03 Dow Corning Insulation panels
CN106752561A (zh) * 2016-11-14 2017-05-31 北京卫星制造厂 一种气凝胶复合隔热涂料及其制备方法
CN106830990B (zh) * 2017-01-13 2020-04-10 伊科纳诺（北京）科技发展有限公司 一种多孔地质聚合物/气凝胶复合隔热材料及制备方法
CN108658623A (zh) * 2017-03-30 2018-10-16 中国矿业大学(北京) 一种含二氧化硅气凝胶常温养护发泡保温板及其制备方法
CN107344863A (zh) * 2017-07-26 2017-11-14 浙江大学 一种基于粉煤灰的地质聚合物多孔保温材料及其制备方法
CN109485315A (zh) * 2018-12-14 2019-03-19 深圳市地聚科技有限公司 一种SiO2气凝胶/多孔地聚物复合保温板的制备方法
CN109762414A (zh) * 2018-12-25 2019-05-17 广东青龙建筑工程有限公司 基于二氧化硅气凝胶改性的保温隔热防水涂料及其制备方法
CN110054918A (zh) * 2019-05-09 2019-07-26 平顶山学院 一种抗开裂无机保温涂料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130010575A (ko) * 2011-07-19 2013-01-29 안영화 에너지 절감 및 건강기능을 위한 건축용 판재 조성물, 그의 제조방법 및 이에 따라 제조된 판재
CN104302597A (zh) * 2012-03-30 2015-01-21 陶氏环球技术有限责任公司 地聚合物前体-气凝胶组合物
US20150102540A1 (en) * 2012-05-09 2015-04-16 Shawcor Ltd. Thermal Insulating Concrete Composition
CN104725958A (zh) * 2015-03-23 2015-06-24 苏州市神龙门窗有限公司 一种户外门窗的隔热涂料及其制备方法
CN107117625A (zh) * 2017-06-19 2017-09-01 浙江省普瑞科技有限公司 一种高透光率二氧化硅气凝胶的制备方法
CN110563438A (zh) * 2019-10-10 2019-12-13 湖北三江航天红阳机电有限公司 一种疏水铝硅气凝胶隔热材料的制备方法
CN112852196A (zh) * 2021-01-11 2021-05-28 中广核研究院有限公司 气凝胶涂料及其制备方法和气凝胶涂层及其制备方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115637061A (zh) * 2022-10-11 2023-01-24 航天特种材料及工艺技术研究所 一种高性能隔热涂层用隔热填料的制备方法
CN115637061B (zh) * 2022-10-11 2024-05-07 航天特种材料及工艺技术研究所 一种高性能隔热涂层用隔热填料的制备方法
CN115849863A (zh) * 2022-11-23 2023-03-28 江苏朗耐德耐火材料有限公司 一种耐火型气凝胶复合保温材料及其制备方法
CN115849863B (zh) * 2022-11-23 2024-03-01 江苏朗耐德耐火材料有限公司 一种耐火型气凝胶复合保温材料及其制备方法
CN118164720A (zh) * 2024-03-12 2024-06-11 湖南工程学院 一种气凝胶-玻化微珠保温砂浆及其制备方法
CN118666558A (zh) * 2024-07-09 2024-09-20 河南兴安新型建筑材料有限公司 一种柔性气凝胶保温砌块及其制备方法

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