CN114479602A - Repair coating for aerogel surface defects and preparation method and application thereof - Google Patents

Repair coating for aerogel surface defects and preparation method and application thereof Download PDF

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CN114479602A
CN114479602A CN202210310698.1A CN202210310698A CN114479602A CN 114479602 A CN114479602 A CN 114479602A CN 202210310698 A CN202210310698 A CN 202210310698A CN 114479602 A CN114479602 A CN 114479602A
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fiber
aerogel
phenolic
coating
phenolic resin
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CN114479602B (en
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黄秀波
张杨
刘圆圆
李文静
孙同臣
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Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention provides a repair coating for aerogel surface defects, a preparation method and an application thereof, which are applied to a surface to be repaired of a phenolic aerogel material, wherein the repair coating comprises the following components in percentage by mass: 10-70% of phenolic resin solution, 10-30% of aerogel, 10-30% of nano inorganic oxide and 10-30% of inorganic fiber. The repair coating provided by the invention can be used for repairing the defects of phenolic aerogel materials, is simple to operate, has excellent matching property with the phenolic aerogel materials, and has excellent maintainability and ablation resistance.

Description

Repair coating for aerogel surface defects and preparation method and application thereof
Technical Field
The invention relates to the technical field of coatings, in particular to a repair coating for aerogel surface defects and a preparation method and application thereof.
Background
The aerogel is a porous three-dimensional network structure constructed by interconnecting gel particles, and is widely applied to the fields of adsorption, separation, catalysis, energy conversion, storage and the like due to the characteristics of low density, high porosity, large specific surface area, low heat conductivity coefficient and the like. The phenolic aerogel is a porous and organic material with a gel network formed by phenolic polymer molecular chains. The phenolic resin has the characteristics of heat resistance, high carbon residue, flame retardance and the like, the phenolic aerogel is injected into a boundary layer in the ablation process to generate a thermal blockage effect, and the pyrolytic carbon layer dissipates heat through a reverse radiation effect; furthermore, as the phenolic aerogel and the carbon aerogel obtained by pyrolysis thereof have lower heat conductivity coefficient, the phenolic aerogel and the carbon aerogel can generate heat insulation effect for a longer time; and the phenolic aerogel has low cost. Therefore, the phenolic aerogel becomes a high-temperature heat insulation and heat protection material with wide application prospect in the high-temperature environment of aerospace.
However, after the phenolic aerogel is knocked during use and processing, the surface of the material is prone to generating defects such as pits and cracks, and the defects even seriously reduce the mechanical property of the material, so that the rejection rate of the material is increased sharply, the waste of material resources is caused, and the service life of related products is influenced. Therefore, in order to solve this problem, it is necessary to repair the defective material.
Disclosure of Invention
The embodiment of the invention provides a repair coating for aerogel surface defects, a preparation method and an application thereof.
In a first aspect, the invention provides a repair coating for aerogel surface defects, which is applied to a surface to be repaired of a phenolic aerogel material, wherein the repair coating comprises the following components in percentage by mass: 10-70% of phenolic resin solution, 10-30% of aerogel, 10-30% of nano inorganic oxide and 10-30% of inorganic fiber.
Preferably, the phenolic aerogel material comprises at least one of phenolic aerogel and phenolic aerogel fiber composite material;
the fiber in the phenolic aerogel fiber composite material is carbon fiber, quartz fiber, glass fiber, mullite fiber, alumina fiber, zirconia fiber or high silica fiber; the diameter of the fiber is 1-100 μm.
Preferably, the aerogel is a phenolic aerogel powder;
the grain diameter of the aerogel is 10 nm-10 mu m.
Preferably, the nano inorganic oxide is selected from Al2O3、SiO2、TiO2、ZrO2、ZnO2At least one of;
the particle size of the nano inorganic oxide is 1-100 nm.
Preferably, the inorganic fiber is at least one selected from carbon fiber, quartz fiber, glass fiber, mullite fiber, alumina fiber and high silica fiber;
the diameter of the fiber is 1-100 μm.
Preferably, the preparation method of the phenolic resin solution comprises the following steps: adding phenolic resin into a solvent, stirring and dissolving, then adding a curing agent, and uniformly stirring to obtain the phenolic resin solution.
Preferably, the stirring speed is 50-1000 rpm, and the stirring time is 2-10 h.
Preferably, the solvent is at least one selected from methanol, ethanol, isopropanol, acetone, acetonitrile, diethyl ether, and tetrahydrofuran.
Preferably, the dosage of the solvent is 20-60% of the dosage of the phenolic resin.
Preferably, the amount of the curing agent is 0.5-5% of the amount of the phenolic resin.
Preferably, the viscosity of the repair coating is 5000-50000 mPas.
In a second aspect, the present invention provides a method for preparing the repair paint of the first aspect, the method comprising:
and adding the nano inorganic oxide and the aerogel into the phenolic resin solution, uniformly stirring, adding the inorganic fiber, uniformly stirring, and obtaining the repairing coating.
In a third aspect, the present invention provides an application of the repair coating according to the first aspect or the repair coating obtained by the preparation method according to the second aspect, wherein the repair coating is applied to a surface to be repaired of a phenolic aerogel material, and the repair of the phenolic aerogel material containing defects is completed after curing.
Preferably, the curing conditions are: curing for 2-6 h at 80-120 ℃.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the repair coating for repairing the defects of the phenolic aerogel materials, provided by the invention, the phenolic resin solution is used as a dispersion phase, and the phenolic aerogel is added into the dispersion phase, so that the repair coating and a defect matrix have excellent matching performance, and cracking failure and the like possibly caused by the difference between the thermal expansion coefficients of the matrix and the repair coating at a high temperature are avoided; meanwhile, inorganic fibers are used as a framework for supporting the repairing coating, and nano inorganic oxides are used as high-temperature resistant components, so that after the phenolic resin component in the repairing coating is ablated, the repaired area still can keep a complete structure by virtue of the inorganic fibers, the profile of the repaired area is not greatly influenced, the structural strength of the repaired area is ensured, and the heat insulation ablation performance of the repairing area is kept by virtue of the nano inorganic oxides.
(2) According to the invention, the phenolic aerogel materials with defects are repaired by the repair coating, so that the rejection rate of the materials is reduced, the service life of related products is prolonged, and the mechanical property and the thermal insulation ablation property of the materials can be ensured after repair.
(3) The preparation method of the repair coating is simple, the repair operation process is simple, the defects can be filled by utilizing the fluidity of the repair coating, the use is more convenient, the labor and time cost are greatly saved, and the economic and social benefits are achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The embodiment of the invention provides a repair coating for aerogel surface defects, which is applied to a surface to be repaired of a phenolic aerogel material, and the repair coating comprises the following components in percentage by mass: 10-70% (for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%) of a phenolic resin solution, 10-30% (for example, 10%, 15%, 20%, 25%, or 30%) of an aerogel, 10-30% (for example, 10%, 15%, 20%, 25%, or 30%) of a nano inorganic oxide, and 10-30% (for example, 10%, 15%, 20%, 25%, or 30%) of an inorganic fiber.
According to the invention, the phenolic resin solution is used as a disperse phase, and the phenolic aerogel is added into the disperse phase, so that the repairing coating and the defect matrix have excellent matching performance, and cracking failure and the like possibly caused by the difference between the thermal expansion coefficients of the matrix and the repairing coating at high temperature are avoided; meanwhile, inorganic fibers are used as a framework for supporting the repair coating, and nano inorganic oxides are used as high-temperature resistant components, so that after the phenolic resin component in the repair coating is ablated, the repaired area still can keep a complete structure by virtue of the inorganic fibers, the structural strength of the repaired area is further ensured, and the heat insulation ablation performance of the repair area is kept by virtue of the nano inorganic oxides.
The sum of the mass fractions of the components in the repair coating is 100%. The surface to be repaired is a surface with defects such as gaps, pits and damages caused by external force such as collision and impact.
In the present invention, the inventors have found that when the mass fraction of the phenolic resin solution satisfies the above range, if the mass fraction of the aerogel is higher than 30%, the content of the aerogel is too high, which results in too much phenolic resin component, and the content of the inorganic fiber and the nano inorganic oxide is too low, which may result in too low structural strength or poor ablation resistance in the repaired area after the phenolic resin component is ablated; if the mass fraction of the aerogel is less than 10%, although the structural strength and ablation resistance of the repaired region after ablation can be ensured, cracks may occur due to a mismatch in the coefficient of thermal expansion with the matrix. Similarly, if the mass fraction of the phenolic resin solution is less than 10%, the content of other components is relatively high, so that the dissolution of other components is not facilitated, and the performance of the prepared repair coating cannot be ensured; if the mass fraction of the phenolic resin solution is more than 70%, the viscosity of the prepared repair coating is too high, which makes the repair operation inconvenient, and the structural strength and ablation resistance of the repaired substrate cannot be ensured due to too small mass fraction of other components.
According to some preferred embodiments, the phenolic aerogel-like material comprises at least one of phenolic aerogel, phenolic aerogel fiber composite;
the fiber in the phenolic aerogel fiber composite material is carbon fiber, quartz fiber, glass fiber, mullite fiber, alumina fiber, zirconia fiber or high silica fiber; the diameter of the fiber is 1 to 100 μm (for example, 1 μm, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 95 μm, or 100 μm).
At least one of them is a mixture of any one or any several of them mixed in any ratio. The phenolic aerogel, mixture of phenolic aerogel fiber composites may also be referred to as a hybrid phenolic aerogel material.
According to the invention, the diameter of the fiber in the phenolic aerogel fiber composite material is limited to 1-100 μm, so that the problem of too low matrix skeleton strength caused by too thin fiber can be avoided, and the problem of poor dispersibility in the matrix caused by too thick and high density fiber can be avoided.
According to some preferred embodiments, the aerogel is a phenolic aerogel powder;
the aerogel has a particle size of 10nm to 10 μm (for example, 10nm, 20nm, 50nm, 100nm, 200nm, 500nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm may be used).
In the invention, the aerogel with the same component as the base body of the surface to be repaired is selected, so that the function of matching the thermal expansion coefficient can be achieved, and the cracking failure possibly caused by the difference of the thermal expansion coefficients between the base body and the repair coating at high temperature can be avoided. It is noted that the aerogel may be obtained by home-made or purchased means. The grain size of the aerogel is limited to 10 nm-10 mu m, which is more beneficial to ensuring the compactness of the repaired part and the flatness of the surface of the repaired part.
According to some more preferred embodiments, the aerogel selected is the same composition as the phenolic aerogel-like material.
In the present invention, the thermal expansion coefficient of the aerogel selected by the repair coating is matched with that of the substrate to be repaired (i.e. the phenolic aerogel material) when the composition of the aerogel is the same.
According to some preferred embodiments, preferably, the nano inorganic oxide is selected from Al2O3、SiO2、TiO2、ZrO2、ZnO2At least one of;
the particle size of the nano inorganic oxide is 1-100 nm (for example, 1nm, 2nm, 5nm, 4 μm, 10nm, 20nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100 nm).
In the present invention, the particle size of the nano inorganic oxide is limited to 1 to 100nm in order to avoid the influence of the excessive particle size of the nano inorganic oxide on the dispersion of the aerogel powder.
According to some preferred embodiments, preferably, the inorganic fiber is at least one selected from the group consisting of carbon fiber, quartz fiber, glass fiber, mullite fiber, alumina fiber, and high silica fiber;
the diameter of the fiber is 1 to 100 μm (for example, 1 μm, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 95 μm, or 100 μm).
In the invention, the diameter of the inorganic fiber is limited to 1-100 μm, so that the problem of too low skeleton strength caused by too thin fiber can be avoided, and the problem of poor dispersibility in the repair coating due to too thick and high density fiber can be avoided, thereby ensuring that the repair coating has certain skeleton and ablation resistance.
According to some more preferred embodiments, when the phenolic aerogel-based material is a phenolic aerogel fiber composite, when the aerogel selected is the same as the phenolic aerogel-based material in composition, it is preferred that the nano-inorganic oxide and the inorganic fiber are both the same in composition as the phenolic aerogel-based material.
According to some preferred embodiments, preferably, the preparation method of the phenolic resin solution comprises: adding phenolic resin into a solvent, stirring and dissolving, then adding a curing agent, and uniformly stirring to obtain the phenolic resin solution.
The phenolic resin selected in the present invention includes, but is not limited to, common phenolic resin and modified phenolic resin (boron phenolic, barium phenolic), and the molecular weight includes, but is not limited to, 800 to 1500 (for example, may be 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, etc.).
According to some preferred embodiments, the stirring speed is 50 to 1000rpm (for example, 50rpm, 100rpm, 200rpm, 500rpm, 600rpm, 800rpm or 1000rpm is possible), and the stirring time is 2 to 10 hours (for example, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours or 10 hours is possible).
According to some preferred embodiments, the solvent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone, acetonitrile, diethyl ether, tetrahydrofuran.
According to some preferred embodiments, the solvent is used in an amount of 20 to 60% (e.g., may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%) of the amount of the phenolic resin.
In the invention, in order to ensure that the phenolic resin has certain rotational viscosity while being dissolved, the dosage of the solvent is limited to be 20-60% of the dosage of the phenolic resin.
According to some preferred embodiments, the curing agent is used in an amount of 0.5 to 5% (e.g., may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%) of the amount of the phenolic resin.
According to some preferred embodiments, the viscosity of the refinish coating is 5000 to 50000 mPas (for example, 5000 mPas, 5500 mPas, 6000 mPas, 8000 mPas, 10000 mPas, 15000 mPas, 20000 mPas, 25000 mPas, 30000 mPas, 35000 mPas, 40000 mPas, 45000 mPas or 50000 mPas may be used).
In the invention, in the actual repairing process, if the viscosity of the repairing coating is too low, the repairing coating is easy to overflow a defect area and is not beneficial to repairing; if the viscosity of the repair coating is too high, the mixing and dispersion of the aerogel powder, the nano inorganic oxide and the inorganic fiber are not facilitated in the preparation process of the repair coating. Therefore, the viscosity of the repair coating material of the present invention is preferably 5000 to 50000 mPas.
The invention also provides a preparation method of the repair coating, the repair coating provided by the invention is prepared by the preparation method, and the preparation method comprises the following steps:
and adding the nano inorganic oxide and the aerogel into the phenolic resin solution, uniformly stirring, adding the inorganic fiber, uniformly stirring, and obtaining the repairing coating.
According to some preferred embodiments, the stirring speed is 50 to 1000rpm (for example, 50rpm, 100rpm, 200rpm, 500rpm, 600rpm, 800rpm or 1000rpm is possible), and the stirring time is 2 to 10 hours (for example, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours or 10 hours is possible).
The invention also provides application of the repair coating, wherein the repair coating provided by the invention is coated on the surface to be repaired of the phenolic aerogel material, and the repair of the phenolic aerogel material containing the defects is completed after curing.
According to some more preferred embodiments, the curing conditions are: curing at 80 to 120 ℃ (for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃) for 2 to 6 hours (for example, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours).
In the present invention, the repair paint is cured while the solvent in the paint is volatilized.
In order to more clearly illustrate the technical solution and advantages of the present invention, a repair coating for aerogel surface defects is described in detail by using several embodiments.
Example 1
The repair coating comprises the following components in percentage by mass: 35% of phenolic resin solution, 15% of aerogel, 20% of nano inorganic oxide and 30% of inorganic fiber;
the preparation method comprises the following steps:
(1) adding phenolic resin into a solvent (acetone), stirring for dissolving, stirring for 3 hours at a rotating speed of 250r/min for dissolving and dispersing, adding a curing agent (aniline), and continuously stirring for 3 hours at a rotating speed of 250r/min for uniformly mixing to obtain a phenolic resin solution;
the using amount of acetone accounts for 30% of the using amount of the phenolic resin, and the using amount of aniline accounts for 0.8% of the using amount of the phenolic resin;
(2) firstly, aerogel (phenolic aerogel powder with the particle size of 50nm) and nano inorganic oxide (SiO with the particle size of 30 nm) are mixed according to the proportion2Powder) is added into the phenolic resin solution obtained in the step (1), stirring and mixing are carried out for 0.5h at the rotating speed of 350r/min, the dispersion is uniform, then inorganic fibers (quartz fibers with the diameter of 3-8 mu m) are added into the mixed solution, and stirring and mixing are carried out for 3h at the rotating speed of 300r/min after mixing, so as to obtain the repair coating; wherein the repair coating has a rotational viscosity of 9340 mPas.
The application comprises the following steps:
filling the repairing paint into the defect parts such as pits, cracks and the like on the surface of the phenolic aerogel quartz fiber composite material in a blade coating mode, and drying at 100 ℃ for 3h to finish the repairing of the phenolic aerogel materials containing the defects.
Example 2
The repair coating comprises the following components in percentage by mass: 40% of phenolic resin solution, 10% of aerogel, 20% of nano inorganic oxide and 30% of inorganic fiber;
the preparation method comprises the following steps:
(1) adding phenolic resin into a solvent (isopropanol), stirring for dissolving, stirring for 3 hours at the rotating speed of 300r/min for dissolving and dispersing, adding a curing agent (hexamethylenetetramine), and continuously stirring at the rotating speed of 300r/min for 4.5 hours for uniformly mixing to obtain a phenolic resin solution;
the dosage of the isopropanol accounts for 40 percent of the dosage of the phenolic resin, and the dosage of the hexamethylenetetramine accounts for 1 percent of the dosage of the phenolic resin;
(2) firstly, aerogel (phenolic aerogel powder with the particle size of 80nm) and nano inorganic oxide (Al with the particle size of 30 nm) are mixed according to the proportion2O3Powder) is added into the phenolic resin solution obtained in the step (1), stirring and mixing are carried out for 0.5h at the rotating speed of 350r/min, the dispersion is uniform, then inorganic fibers (alumina fibers with the diameter of 5-10 mu m) are added into the mixed solution, and stirring and mixing are carried out for 3h at the rotating speed of 350r/min after mixing, so as to obtain the repair coating; wherein the repair coat has a rotational viscosity of 8670 mPas.
The application comprises the following steps:
filling the repairing paint into the defect parts such as pits, cracks and the like on the surface of the phenolic aerogel alumina fiber composite material in a blade coating mode, and drying at 80 ℃ for 3h to finish the repairing of the phenolic aerogel materials containing the defects.
Example 3
The repair coating comprises the following components in percentage by mass: 70% of phenolic resin solution, 10% of aerogel, 10% of nano inorganic oxide and 10% of inorganic fiber;
the preparation method comprises the following steps:
(1) adding phenolic resin into a solvent (ethanol), stirring for dissolving, stirring for 2 hours at a rotating speed of 500r/min for dissolving and dispersing, adding a curing agent (paraformaldehyde), and continuously stirring for 2 hours at a rotating speed of 500r/min for uniformly mixing to obtain a phenolic resin solution;
the using amount of the ethanol accounts for 60% of the using amount of the phenolic resin, and the using amount of the paraformaldehyde accounts for 5% of the using amount of the phenolic resin;
(2) firstly, mixing the aerogel (phenolic aerogel powder) according to the above-mentioned mixing ratioParticle diameter of 1 μm), and a nano inorganic oxide (ZrO having a particle diameter of 100nm)2Powder) is added into the phenolic resin solution obtained in the step (1), stirring and mixing are carried out for 0.5h at the rotating speed of 550r/min, the dispersion is uniform, inorganic fibers (zirconia fibers with the diameter of 50-100 mu m) are added into the mixed solution, and stirring and mixing are carried out continuously for 4h at the rotating speed of 550r/min after mixing, so as to obtain the repair coating; wherein the repair coat has a rotational viscosity of 3220 mPas.
The application comprises the following steps:
filling the repairing paint into the defect parts such as pits, cracks and the like on the surface of the phenolic aerogel zirconia fiber composite material in a blade coating mode, and drying at 120 ℃ for 2h to finish the repairing of the phenolic aerogel material containing the defects.
Example 4
The repair coating comprises the following components in percentage by mass: 12% of phenolic resin solution, 30% of aerogel, 29% of nano inorganic oxide and 29% of inorganic fiber;
the preparation method comprises the following steps:
(1) adding phenolic resin into a solvent (acetonitrile), stirring for dissolving, stirring for 2 hours at the rotating speed of 600r/min for dissolving and dispersing, then adding a curing agent (aniline), and continuously stirring for 2 hours at the rotating speed of 600r/min for uniformly mixing to obtain a phenolic resin solution;
the using amount of acetonitrile accounts for 20% of the using amount of the phenolic resin, and the using amount of aniline accounts for 0.5% of the using amount of the phenolic resin;
(2) firstly, aerogel (phenolic aerogel powder with the particle size of 10 mu m) and nano inorganic oxide (SiO with the particle size of 1-5 nm) are mixed according to the proportion2Powder) is added into the phenolic resin solution obtained in the step (1), stirring and mixing are carried out for 0.5h at the rotating speed of 400r/min, the dispersion is uniform, inorganic fibers (glass fibers with the diameter of 1-10 mu m) are added into the mixed solution, and stirring and mixing are carried out for 4h at the rotating speed of 400r/min after mixing, so as to obtain the repair coating; wherein the repair coat has a rotational viscosity of 48560 mPas.
The application comprises the following steps:
filling the repairing paint into the defect parts such as pits, cracks and the like on the surface of the phenolic aerogel glass fiber composite material in a blade coating mode, and drying at 85 ℃ for 6 hours to finish the repairing of the phenolic aerogel materials containing the defects.
Example 5
Example 5 is essentially the same as example 1, except that: the nano inorganic oxide is ZnO2The inorganic fiber is carbon fiber.
Comparative example 1
The repair coating comprises the following components in percentage by mass: 35% of phenolic resin solution, 35% of nano inorganic oxide and 30% of inorganic fiber;
the preparation method comprises the following steps:
(1) adding phenolic resin into a solvent (acetone), stirring for dissolving, stirring for 3 hours at a rotating speed of 250r/min for dissolving and dispersing, adding a curing agent (aniline), and continuously stirring for 3 hours at a rotating speed of 250r/min for uniformly mixing to obtain a phenolic resin solution;
the using amount of acetone accounts for 30% of the using amount of the phenolic resin, and the using amount of aniline accounts for 0.8% of the using amount of the phenolic resin;
(2) firstly, nano inorganic oxide (SiO with the grain diameter of 30 nm) is mixed according to the above proportion2Powder) is added into the phenolic resin solution obtained in the step (1), stirring and mixing are carried out for 0.5h at the rotating speed of 350r/min, the dispersion is uniform, then inorganic fibers (quartz fibers with the diameter of 3-8 mu m) are added into the mixed solution, and stirring and mixing are carried out for 3h at the rotating speed of 300r/min after mixing, so as to obtain the repair coating; wherein the repair coat has a rotational viscosity of 4560 mPas.
The application comprises the following steps:
filling the repairing paint into the defect parts such as pits, cracks and the like on the surface of the phenolic aerogel quartz fiber composite material in a blade coating mode, and drying at 100 ℃ for 3h to finish the repairing of the phenolic aerogel materials containing the defects.
Comparative example 2
The repair coating comprises the following components in percentage by mass: 40% of phenolic resin solution, 30% of aerogel and 30% of nano inorganic oxide;
the preparation method comprises the following steps:
(1) adding phenolic resin into a solvent (isopropanol), stirring for dissolving, stirring for 3 hours at the rotating speed of 300r/min for dissolving and dispersing, adding a curing agent (hexamethylenetetramine), and continuously stirring at the rotating speed of 300r/min for 4.5 hours for uniformly mixing to obtain a phenolic resin solution;
the dosage of the isopropanol accounts for 40 percent of the dosage of the phenolic resin, and the dosage of the hexamethylenetetramine accounts for 1 percent of the dosage of the phenolic resin;
(2) firstly, aerogel (phenolic aerogel powder with the particle size of 80nm) and nano inorganic oxide (Al with the particle size of 30 nm) are mixed according to the proportion2O3Powder) is added into the phenolic resin solution obtained in the step (1), stirred and mixed for 0.5h at the rotating speed of 350r/min, and dispersed uniformly to obtain the repair coating; wherein the repair coat has a rotational viscosity of 4840 mPas.
The application comprises the following steps:
filling the repairing paint into the defect parts such as pits, cracks and the like on the surface of the phenolic aerogel alumina fiber composite material in a blade coating mode, and drying at 80 ℃ for 3h to finish the repairing of the phenolic aerogel materials containing the defects.
Comparative example 3
Comparative example 3 is substantially the same as example 4 except that: the repair coating comprises the following components in percentage by mass: 10% of phenolic resin solution, 32% of aerogel, 27% of nano inorganic oxide and 31% of inorganic fiber.
The repair coatings prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to a thermal test, and the results of the thermal test are shown in table 1. It should be noted that the thermal test conditions of examples 1 to 5 and comparative example 1 are: placing the repaired phenolic aerogel material in an aerobic environment at 1000 ℃ for 4 hours; and comparative example 2 was subjected to the thermal test conditions: and (3) placing the repaired phenolic aerogel material in an aerobic environment at 800 ℃ for 4 h.
TABLE 1
Figure BDA0003568092520000111
Figure BDA0003568092520000121
Wherein, the surface state in the thermal examination is intact, which means that the surface state of the repaired part is consistent with the surface state of the unrepaired part after the thermal examination, and the structure of the repaired part can be maintained; the loose structure means that the repaired part can not maintain a certain shape after thermal examination, and the loose structure causes the repaired part to fall off. In comparative example 3, since the repair paint was not in a fluid state but in a solid-fluid state and had no fluidity, it could not be used as a repair paint, and repair and thermal examination could not be performed.
As can be seen from Table 1, the repair coating prepared by the embodiment of the invention keeps the repaired part intact after being subjected to the thermal examination in the aerobic environment of 1000 ℃ for 4 hours, the conditions of falling off, damage and the like do not occur, and the surface state is consistent with that of the unrepaired part. However, the repair coating of comparative example 1 is not added with aerogel, after the thermal examination in an aerobic environment of 1000 ℃ for 4 hours, the repaired part cracks and is damaged, mainly the repair coating lacks the same composition as the matrix (phenolic aerogel quartz fiber composite), and the thermal expansion coefficient between the repair coating and the matrix is mismatched, so that the repaired part cracks and the like; similarly, the repair coating of comparative example 2 is not added with inorganic fibers, the repaired part completely falls off after the thermal examination for 4 hours in an aerobic environment at 800 ℃, the damage is serious, and the internal matrix also has a serious oxidation phenomenon, because the inorganic fibers are not used as the support framework of the coating, the phenolic component is ablated after the thermal examination, and the residual inorganic nano particles can not maintain a certain shape and have loose structures, so that the repaired part completely falls off.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The repair coating for the surface defects of the aerogel is characterized by being applied to the surface to be repaired of a phenolic aerogel material, wherein the repair coating comprises the following components in percentage by mass: 10-70% of phenolic resin solution, 10-30% of aerogel, 10-30% of nano inorganic oxide and 10-30% of inorganic fiber.
2. The refinish coating of claim 1 wherein:
the phenolic aerogel material comprises at least one of phenolic aerogel and phenolic aerogel fiber composite material;
the fiber in the phenolic aerogel fiber composite material is carbon fiber, quartz fiber, glass fiber, mullite fiber, alumina fiber, zirconia fiber or high silica fiber; the diameter of the fiber is 1-100 μm.
3. The refinish coating of claim 1 wherein:
the aerogel is phenolic aerogel powder;
the grain size of the aerogel is 10 nm-10 mu m; and/or
The nano inorganic oxide is selected from Al2O3、SiO2、TiO2、ZrO2、ZnO2At least one of;
the particle size of the nano inorganic oxide is 1-100 nm.
4. The refinish coating of claim 1 wherein:
the inorganic fiber is at least one selected from carbon fiber, quartz fiber, glass fiber, mullite fiber, alumina fiber and high silica fiber;
the diameter of the fiber is 1-100 μm.
5. The refinish coating of claim 1 wherein:
the preparation method of the phenolic resin solution comprises the following steps: adding phenolic resin into a solvent, stirring and dissolving, then adding a curing agent, and uniformly stirring to obtain a phenolic resin solution;
preferably, the stirring speed is 50-1000 rpm, and the stirring time is 2-10 h.
6. The refinish coating of claim 5 wherein:
the solvent is at least one selected from methanol, ethanol, isopropanol, acetone, acetonitrile, diethyl ether and tetrahydrofuran; and/or
The curing agent is at least one selected from hexamethylenetetramine, aniline and paraformaldehyde.
7. The refinish coating according to claim 5 or 6, wherein:
the dosage of the solvent is 20-60% of that of the phenolic resin; and/or
The dosage of the curing agent is 0.5-5% of that of the phenolic resin.
8. The refinish coating of claim 1, wherein:
the viscosity of the repair coating is 5000-50000 mPas.
9. A method of preparing a refinish coating according to any one of claims 1 to 8, said method comprising:
and adding the nano inorganic oxide and the aerogel into the phenolic resin solution, uniformly stirring, adding the inorganic fiber, uniformly stirring, and obtaining the repairing coating.
10. Use of a refinish coating according to any one of claims 1 to 8 or obtained according to the method of claim 9,
coating the repairing coating on the surface to be repaired of the phenolic aerogel material, and completing repairing of the phenolic aerogel material containing the defects after curing;
preferably, the curing conditions are: curing for 2-6 h at 80-120 ℃.
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