CN108003783B - Organic-inorganic hybrid hole sealing agent for plasma spraying ceramic coating, and preparation method and application thereof - Google Patents

Organic-inorganic hybrid hole sealing agent for plasma spraying ceramic coating, and preparation method and application thereof Download PDF

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CN108003783B
CN108003783B CN201711214335.3A CN201711214335A CN108003783B CN 108003783 B CN108003783 B CN 108003783B CN 201711214335 A CN201711214335 A CN 201711214335A CN 108003783 B CN108003783 B CN 108003783B
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hole sealing
sealing agent
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CN108003783A (en
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汪米琪
易于
吴林涛
周泽华
王泽华
江少群
王刚
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Hohai University HHU
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica

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Abstract

The invention discloses an organic-inorganic hybrid hole sealing agent for a plasma spraying ceramic coating, which comprises a precursor A, a methyl silicone resin film forming agent B, absolute ethyl alcohol, ammonia water and deionized water, wherein the precursor A comprises tetraethoxysilane and methyltriethoxysilane, the molar ratio of the tetraethoxysilane to the methyltriethoxysilane is 100: 60 ~ 200, the molar ratio of the precursor A to the absolute ethyl alcohol to the ammonia water to the deionized water is 1: 30 ~ 35: 2 ~ 3: 5 ~ 7, and the addition amount of the methyl silicone resin film forming agent B accounts for 1 ~ 5% of the total mass of the organic-inorganic hybrid hole sealing agent for the coating.

Description

Organic-inorganic hybrid hole sealing agent for plasma spraying ceramic coating, and preparation method and application thereof
Technical Field
The invention relates to an organic-inorganic hybrid hole sealing agent for a plasma sprayed ceramic coating, a preparation method and application thereof, belonging to the technical field of material corrosion and protection.
Background
The plasma spraying ceramic coating has the characteristics of high hardness, good wear resistance and the like, and is widely applied to the fields of aviation, machinery, mines and the like, but the plasma spraying ceramic coating usually has 5% ~ 8% of holes which cannot be eliminated by means of a process technology, and the holes can be used as corrosion channels in a complex corrosion environment to corrode a metal matrix under the ceramic coating.
The most commonly used coating hole sealing agent at present is an organic hole sealing agent and has the advantages of good hole sealing effect, good toughness, high strength, good corrosion resistance and the like. Such as literature (Jingking Zhang, Zehua Wang, Pinghua Lin, etc. effective of sealing treatment on correction resistance of plasma-dispersed NiCrAl/Cr)2O3-8wt.%TiO2 Coating[J]Journal of Thermal technology 2011.20 (3): 508-2O3-8wt.%TiO2The coating is subjected to hole sealing treatment, and a salt spray corrosion test proves that: the corrosion weight loss of the coating without hole sealing is 49 times higher than that of the coating with the organic silicon resin hole sealing.
The waterproof biological adsorption material commonly used at present is mainly a coating type material. For example, in the 'antifouling paint and method of preparing the same' (201410449421.2), the paint components include one or more of capsaicin, isothiazolinone, eucalyptus extract and marine invertebrate extract, and have a low surface energy, so that marine organisms do not attach to the surface of the paint. However, for plasma spraying ceramic coatings, it is a major function to improve the wear resistance of the workpiece. Under the abrasion working condition, the anti-biosorption coating is extremely easy to rapidly abrade and fall off, and cannot play a role in preventing the biosorption on the surface of the plasma spraying ceramic coating.
As for the hole sealing treatment of the plasma spraying ceramic coating, if the sealing material not only has excellent effect of sealing the pores of the coating, but also has the function of improving the water-proof biological adsorption of the coating, the process steps are greatly reduced, the cost is reduced, and the hole-sealed coating can play a long-acting protection effect on the workpiece used in the water environment, thereby expanding the application range of the coated workpiece.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide an organic-inorganic hybrid hole sealing agent for a plasma sprayed ceramic coating, a preparation method and application thereof. The hole sealing agent is reasonably prepared by component design and process, a micron-nano structure is constructed to improve the hydrophobicity of the hole sealing agent, a hole sealing coating has the functions of corrosion resistance and water-proof biosorption, the hole sealing effect is equivalent to that of organic silicon resin, the electrochemical corrosion potential of the coating after hole sealing is similar to that of a similar coating after hole sealing of the organic silicon resin, the corrosion current is obviously smaller than that of the similar coating after hole sealing of the organic silicon resin, and the water-proof biosorption performance is obviously superior to that of the similar coating after hole sealing of the organic silicon resin. The hole sealing agent can play a long-acting protection effect on the plasma spraying ceramic coating used in the water environment. In addition, the surface of the coating after hole sealing is polished to remove redundant surface hole sealing agent, the corrosion resistance and the waterproof biological adsorption effect of the coating are realized by the aid of the hole sealing agent in the micropores, and the wear resistance of the ceramic coating is not affected.
The organic-inorganic hybrid hole sealing agent for the plasma sprayed ceramic coating is characterized by comprising a precursor A, a methyl silicone resin film forming agent B, absolute ethyl alcohol, ammonia water and deionized water, wherein the precursor A comprises tetraethoxysilane and methyl triethoxysilane, the molar ratio of the tetraethoxysilane to the methyl triethoxysilane is 100: 60 ~ 200, the molar ratio of the precursor A to the absolute ethyl alcohol to the ammonia water to the deionized water is 1: 30 ~ 35: 2 ~ 3: 5 ~ 7, and the addition amount of the methyl silicone resin film forming agent B accounts for 1 ~ 5% of the total mass of the organic-inorganic hybrid hole sealing agent for the coating.
Preferably, the precursor A is mixed with absolute ethyl alcohol, ammonia water and deionized water, and a group containing a silica inorganic component in the hole sealing agent is obtained through a hydrolysis reaction process.
The invention also provides a preparation method of the organic-inorganic hybrid hole sealing agent for the plasma spraying ceramic coating, which is characterized by comprising the following steps:
(1) firstly, mixing absolute ethyl alcohol, ammonia water and deionized water, placing the mixture into a constant-temperature water bath kettle at the temperature of 30 ~ 50 ℃, stirring the mixture evenly, adding tetraethoxysilane, keeping the temperature for 1 hour, heating the mixture to the temperature of 50 ~ 70 ℃, adding methyltriethoxysilane, and placing the mixture at normal temperature to obtain mixed sol;
(2) and adding the methyl silicone resin film-forming agent B into the mixed sol, and reacting to obtain the organic-inorganic hybrid hole sealing agent for the plasma sprayed ceramic coating.
Preferably, in the step (1), the molar ratio of the tetraethoxysilane to the methyltriethoxysilane is 100: 60 ~ 200, the tetraethoxysilane and the methyltriethoxysilane form a precursor a, and the molar ratio of the precursor a, the absolute ethyl alcohol, the ammonia water and the deionized water is 1: 30 ~ 35: 2 ~ 3: 5 ~ 7.
Preferably, in the step (1), the mixture is stirred in a precision booster mixer.
Preferably, in the step (1), the mixture is left at room temperature for 24 hours.
Preferably, in the step (2), the addition amount of the methyl silicone resin film forming agent B accounts for 1 ~ 5% of the total mass of the organic-inorganic hybrid hole sealing agent for the plasma spraying ceramic coating.
Preferably, in the step (2), after reacting for 2 hours, the mixture is kept standing at normal temperature for 48 hours for aging treatment.
The application of the organic-inorganic hybrid hole sealing agent for the plasma spraying ceramic coating is characterized in that the hole sealing agent for the coating is used for hole sealing treatment of the plasma spraying ceramic coating, and the specific hole sealing treatment method comprises the following steps:
(1) performing surface pretreatment on the spray coating test piece;
(2) placing a sample into the prepared organic-inorganic hybrid hole sealing agent, soaking for 15min, taking out, brushing surface bubbles with a brush, and repeating the soaking and brushing operations once after brushing;
(3) soaking for 15min again, naturally drying for 15min, placing in a 60 deg.C oven, curing for 30min, taking out, and naturally cooling;
(4) and (3) repeating the steps (2) and (3), then putting the mixture into a 120 ℃ oven for curing for 2h, taking out the test piece, naturally cooling and polishing the test piece to remove the redundant sealant on the surface layer, and finishing the sealing treatment process.
Preferably, the surface pretreatment comprises derusting, sand blasting coarsening, cleaning degreasing and drying.
The hole sealing agent has the advantages that the hole sealing effect is equivalent to that of common organic silicon resin, the electrochemical corrosion potential of the coating after hole sealing is similar to that of a similar coating after organic silicon resin hole sealing, the corrosion current of the coating after hole sealing is obviously smaller than that of the similar coating after organic silicon resin hole sealing, the static hole sealing performance of the coating after hole sealing is 130 ~ 170 degrees, and the waterproof biosorption performance is obviously superior to that of the coating after organic silicon resin hole sealing, and the hole sealing agent can play a role in protecting the plasma spraying ceramic coating used in the same water environment for a long term without influencing the wear resistance of the ceramic coating.
Drawings
FIG. 1 shows plasma sprayed Al with the coating sealer of the present invention2O3-13wt.%TiO2The surface appearance of the coating after the hole sealing of the ceramic coating.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1:
plasma spraying Al2O3-13wt.%TiO2The organic-inorganic hybrid hole sealing agent for the ceramic coating mainly comprises a precursor A, a methyl silicone resin film forming agent B, absolute ethyl alcohol, ammonia water and deionized water, wherein the precursor A comprises tetraethoxysilane and methyl triethoxysilane, and the molar weight ratio of the precursor A to the methyl triethoxysilane is 100: 120, the molar weight ratio of the precursor A, the absolute ethyl alcohol, the ammonia water and the deionized water is 1: 33: 2: 6, the addition of the methyl silicone resin film forming agent B accounts for 3% of the total mass of the organic-inorganic hybrid hole sealing agent for the coating, the precursor A is mixed with absolute ethyl alcohol, ammonia water and deionized water, and a group containing a silica inorganic component in the hole sealing agent is obtained through processes such as hydrolysis reaction and the like.
The preparation method of the organic-inorganic hybrid hole sealing agent for the coating comprises the following steps:
(1) mixing ethanol, ammonia water and deionized water according to the proportion, placing the mixture into a constant-temperature water bath kettle at 40 ℃, adding tetraethoxysilane after stirring the mixture evenly in a precise boosting stirrer, keeping the temperature for 1 hour, heating the mixture to 60 ℃, adding methyltriethoxysilane, and placing the mixture for 24 hours at normal temperature to obtain mixed sol;
(2) and adding the methyl silicone resin film-forming agent B into the mixed sol according to the proportion, reacting for 2 hours, and standing for 48 hours at normal temperature for aging treatment to obtain the organic-inorganic hybrid hole sealing agent for the coating.
The hole sealing agent is used for plasma spraying of Al2O3-13wt.%TiO2The method for sealing the hole of the ceramic coating comprises the following steps:
(1) carrying out surface pretreatment on the spray coating test piece, including derusting, sandblasting and coarsening, cleaning and degreasing and drying;
(2) placing a sample into the prepared organic-inorganic hybrid hole sealing agent, soaking for 15min, taking out, brushing surface bubbles with a brush, and repeating the soaking and brushing operations once after brushing;
(3) soaking for 15min again, naturally drying for 15min, placing in a 60 deg.C oven, curing for 30min, taking out, and naturally cooling;
(4) and (3) repeating the steps (2) and (3), then putting the mixture into a 120 ℃ oven for curing for 2h, taking out the test piece, naturally cooling and polishing the test piece to remove the redundant sealant on the surface layer, and finishing the sealing treatment process.
The hole sealing agent is used for plasma spraying of Al2O3-13wt.%TiO2The method comprises the steps of carrying out hole sealing treatment on a ceramic coating, testing and calculating the porosity of the coating before and after hole sealing by means of TCI metallographic analysis software and adopting a microanalysis method, testing the Tafel polarization curve of the Electrochemical corrosion potential and the corrosion current of the coating by means of a PARSTAT 2273 Advanced Electrochemical System type Electrochemical instrument, testing the static contact angle of the coating by means of a CAM200 optical contact angle instrument, and artificially simulating a aquatic organism environment to be a pond which is designed by a laboratory by self and comprises algae, barnacles, screws and other representative aquatic organisms. As a comparative organic silicon resin hole sealing agent, the hole sealing treatment of the similar coating is carried out by adopting a conventional method. All test and calculation results are the average value of more than three results.
The results show that: spraying Al to the plasma by using the hole sealing agent2O3-13wt.%TiO2After the hole sealing treatment of the ceramic coating, the porosity of the hole sealing coating is 2.4% of that of the unsealed coating, and the electrochemical corrosion potential and the corrosion current are-0.39V and 1.2' 10 respectively-7A×cm-3While the common organic silicon resin hole sealing agent is adopted to spray Al to the plasma2O3-13wt.%TiO2After the ceramic coating is sealed, the porosity of the sealing coating is 3.4% of that of the unsealed coating, and the corrosion potential and the corrosion current are-0.42V and 1.3' 10 respectively- 6A×cm-3I.e. the sealant pair Al2O3-13wt.%TiO2The hole sealing effect of the coating is equivalent to that of an organic silicon resin hole sealing agent, the corrosion potential of the coating after hole sealing of the hole sealing agent is similar to that of the coating after hole sealing of the organic silicon resin, and the corrosion current of the coating after hole sealing of the hole sealing agent is obviously smaller than that of the coating after hole sealing of the organic silicon resin; al after hole sealing of the hole sealing agent2O3-13wt.%TiO2The static contact angle of the coating is 166 degrees, after a 4-month soaking test is carried out in an artificial simulated aquatic environment containing representative aquatic organisms such as algae, barnacles and screws, the coating has no obvious aquatic organism adsorption, and under the same condition, the surface of the coating after the hole sealing of the organic silicon resin hole sealing agent has obvious adsorption of algae, screws and the like, namely Al after the hole sealing of the hole sealing agent2O3-13wt.%TiO2The waterproof biological adsorption performance of the coating is obviously superior to that of the similar coating after the common organic silicon resin is used for hole sealing. The hole sealing agent has the functions of sealing coating pores and improving waterproof biological adsorption of the coating, and can be used for Al in water environment2O3-13wt.%TiO2The plasma spraying ceramic coating has a long-acting protection effect and does not influence the wear resistance of the ceramic coating. (the coating sealant of the invention sprays Al to plasma2O3-13wt.%TiO2The surface appearance of the coating after the sealing of the ceramic coating is shown in figure 1. )
Example 2:
plasma spraying Cr2O3-8wt.%TiO2The organic-inorganic hybrid hole sealing agent for the ceramic coating mainly comprises a precursor A, a methyl silicone resin film forming agent B, absolute ethyl alcohol, ammonia water and deionized water, wherein the precursor A comprises tetraethoxysilane and methyl triethoxysilane, and the molar weight ratio of the precursor A to the methyl triethoxysilane is 100: 200, wherein the molar weight ratio of the precursor A, the absolute ethyl alcohol, the ammonia water and the deionized water is 1: 32: 3: and 7, the addition amount of the methyl silicone resin film forming agent B accounts for 5% of the total mass of the organic-inorganic hybrid hole sealing agent for the coating, the precursor A is mixed with absolute ethyl alcohol, ammonia water and deionized water, and a group containing a silica inorganic component in the hole sealing agent is obtained through processes such as hydrolysis reaction and the like.
The preparation method of the organic-inorganic hybrid hole sealing agent for the coating comprises the following steps:
(1) mixing ethanol, ammonia water and deionized water according to the proportion, placing the mixture into a constant-temperature water bath kettle at 40 ℃, adding tetraethoxysilane after stirring the mixture evenly in a precise boosting stirrer, keeping the temperature for 1 hour, heating the mixture to 60 ℃, adding methyltriethoxysilane, and placing the mixture for 24 hours at normal temperature to obtain mixed sol;
(2) and adding the methyl silicone resin film-forming agent B into the mixed sol according to the proportion, reacting for 2 hours, and standing for 48 hours at normal temperature for aging treatment to obtain the organic-inorganic hybrid hole sealing agent for the coating.
The hole sealing agent is used for plasma spraying of Cr2O3-8wt.%TiO2The method for sealing the hole of the ceramic coating comprises the following steps:
(1) carrying out surface pretreatment on the spray coating test piece, including derusting, sandblasting and coarsening, cleaning and degreasing and drying;
(2) placing a sample into the prepared organic-inorganic hybrid hole sealing agent, soaking for 15min, taking out, brushing surface bubbles with a brush, and repeating the soaking and brushing operations once after brushing;
(3) soaking for 15min again, naturally drying for 15min, placing in a 60 deg.C oven, curing for 30min, taking out, and naturally cooling;
(4) and (3) repeating the steps (2) and (3), then putting the mixture into a 120 ℃ oven for curing for 2h, taking out the test piece, naturally cooling and polishing the test piece to remove the redundant sealant on the surface layer, and finishing the sealing treatment process.
The hole sealing agent is used for spraying Cr to the plasma2O3-8wt.%TiO2The method comprises the steps of sealing holes of the ceramic coating, testing and calculating the porosity of the coating before and after sealing the holes by means of TCI metallographic analysis software and adopting a microanalysis method, testing the Tafel polarization curve of the Electrochemical corrosion potential and the corrosion current of the coating by means of a PARSTAT 2273 Advanced Electrochemical System type Electrochemical instrument, testing the static contact angle of the coating by means of a CAM200 optical contact angle instrument, and artificially simulating a pool which is designed for a laboratory and contains algae, barnacles and snails and is in a hydrobioenvironmentSilk, etc. representative aquatic organisms. As a comparative organic silicon resin hole sealing agent, the hole sealing treatment of the similar coating is carried out by adopting a conventional method. All test and calculation results are the average value of more than three results.
The results show that: the hole sealing agent is used for spraying Cr to the plasma2O3-8wt.%TiO2After the hole sealing treatment of the ceramic coating, the porosity of the hole sealing coating is 2.8% of that of the unsealed coating, and the electrochemical corrosion potential and the corrosion current are-0.42V and 1.4' 10 respectively-7A×cm-3And common organic silicon resin hole sealing agent is adopted to spray Cr to the plasma2O3-8wt.%TiO2After the ceramic coating is sealed, the porosity of the sealing coating is 3.1% of that of the unsealed coating, and the corrosion potential and the corrosion current are-0.40V and 0.7' 10 respectively- 6A×cm-3I.e. the sealant pair Cr2O3-8wt.%TiO2The hole sealing effect of the coating is equivalent to that of an organic silicon resin hole sealing agent, the corrosion potential of the coating after hole sealing of the hole sealing agent is similar to that of the coating after hole sealing of the organic silicon resin, and the corrosion current of the coating after hole sealing of the hole sealing agent is obviously smaller than that of the coating after hole sealing of the organic silicon resin; cr obtained after hole sealing by the hole sealing agent2O3-8wt.%TiO2The static contact angle of the coating is 160 degrees, after a 4-month soaking test is carried out in an artificial simulated aquatic environment containing representative aquatic organisms such as algae, barnacles, screws and the like, the coating does not have obvious aquatic organism adsorption, and under the same condition, the surface of the coating after the sealing of the organic silicon resin sealing agent has obvious adsorption of algae, screws and the like, namely the Cr after the sealing of the sealing agent is carried out2O3-8wt.%TiO2The waterproof biological adsorption performance of the coating is obviously superior to that of the similar coating after the common organic silicon resin is used for hole sealing. The hole sealing agent has the functions of sealing coating pores and improving waterproof biological adsorption of the coating, and can be used for Cr used in water environment2O3-8wt.%TiO2The plasma spraying ceramic coating has a long-acting protection effect and does not influence the wear resistance of the ceramic coating.
Example 3:
plasma spraying ZrO2Organic-inorganic hybrid for ceramic coatingThe main components of the chemical hole sealing agent comprise a precursor A, a methyl silicone resin film former B, absolute ethyl alcohol, ammonia water and deionized water, wherein the precursor A comprises tetraethoxysilane and methyltriethoxysilane, and the molar weight ratio of the precursor A to the methyl silicone resin film former B is 100: 70, the molar weight ratio of the precursor A, the absolute ethyl alcohol, the ammonia water and the deionized water is 1: 31: 2: 5, the addition amount of the methyl silicone resin film forming agent B accounts for 1% of the total mass of the organic-inorganic hybrid hole sealing agent for the coating, the precursor A is mixed with absolute ethyl alcohol, ammonia water and deionized water, and a group containing a silica inorganic component in the hole sealing agent is obtained through processes such as hydrolysis reaction and the like.
The preparation method of the organic-inorganic hybrid hole sealing agent for the coating comprises the following steps:
(1) mixing ethanol, ammonia water and deionized water according to the proportion, placing the mixture into a constant-temperature water bath kettle at 40 ℃, adding tetraethoxysilane after stirring the mixture evenly in a precise boosting stirrer, keeping the temperature for 1 hour, heating the mixture to 60 ℃, adding methyltriethoxysilane, and placing the mixture for 24 hours at normal temperature to obtain mixed sol;
(2) and adding the methyl silicone resin film-forming agent B into the mixed sol according to the proportion, reacting for 2 hours, and standing for 48 hours at normal temperature for aging treatment to obtain the organic-inorganic hybrid hole sealing agent for the coating.
The hole sealing agent is used for plasma spraying ZrO2The method for sealing the hole of the ceramic coating comprises the following steps:
(1) carrying out surface pretreatment on the spray coating test piece, including derusting, sandblasting and coarsening, cleaning and degreasing and drying;
(2) placing a sample into the prepared organic-inorganic hybrid hole sealing agent, soaking for 15min, taking out, brushing surface bubbles with a brush, and repeating the soaking and brushing operations once after brushing;
(3) soaking for 15min again, naturally drying for 15min, placing in a 60 deg.C oven, curing for 30min, taking out, and naturally cooling;
(4) and (3) repeating the steps (2) and (3), then putting the mixture into a 120 ℃ oven for curing for 2h, taking out the test piece, naturally cooling and polishing the test piece to remove the redundant sealant on the surface layer, and finishing the sealing treatment process.
The hole sealing agent is used for spraying ZrO to the plasma2The method comprises the steps of carrying out hole sealing treatment on a ceramic coating, testing and calculating the porosity of the coating before and after hole sealing by means of TCI metallographic analysis software and adopting a microanalysis method, testing the Tafel polarization curve of the Electrochemical corrosion potential and the corrosion current of the coating by means of a PARSTAT 2273 Advanced Electrochemical System type Electrochemical instrument, testing the static contact angle of the coating by means of a CAM200 optical contact angle instrument, and artificially simulating a aquatic organism environment to be a pond which is designed by a laboratory by self and comprises algae, barnacles, screws and other representative aquatic organisms. As a comparative organic silicon resin hole sealing agent, the hole sealing treatment of the similar coating is carried out by adopting a conventional method. All test and calculation results are the average value of more than three results.
The results show that: ZrO is sprayed by the hole sealing agent to plasma2After the hole sealing treatment of the ceramic coating, the porosity of the hole sealing coating is 3.2% of that of the unsealed coating, and the electrochemical corrosion potential and the corrosion current are-0.47V and 0.3' 10 respectively-6A×cm-3And the ZrO is sprayed by plasma by adopting a common organic silicon resin hole sealing agent2After the ceramic coating is sealed, the porosity of the sealing coating is 3.9% of that of the unsealed coating, and the corrosion potential and the corrosion current are-0.52V and 1.0' 10 respectively-6A×cm-3I.e. the sealer to ZrO2The hole sealing effect of the coating is equivalent to that of an organic silicon resin hole sealing agent, the corrosion potential of the coating after hole sealing of the hole sealing agent is similar to that of the coating after hole sealing of the organic silicon resin, and the corrosion current of the coating after hole sealing of the hole sealing agent is obviously smaller than that of the coating after hole sealing of the organic silicon resin; ZrO after hole sealing by the hole sealing agent2The static contact angle of the coating is 145 degrees, after a 4-month soaking test in an artificial simulated aquatic environment containing representative aquatic organisms such as algae, barnacles, screws and the like, the coating has no obvious aquatic organism adsorption, and under the same condition, the surface of the coating after the sealing of the organic silicon resin sealing agent has obvious adsorption of algae, screws and the like, namely ZrO after the sealing of the sealing agent is carried out2The waterproof biological adsorption performance of the coating is obviously superior to that of the similar coating after the common organic silicon resin is used for hole sealing. The hole sealing agent has a sealing coatingThe pores and the function of improving the waterproof biological adsorption of the coating can be improved, and ZrO can be used in water environment2The plasma spraying ceramic coating has a long-acting protection effect and does not influence the wear resistance of the ceramic coating.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (6)

1. An organic-inorganic hybrid hole sealing agent for a plasma sprayed ceramic coating is characterized by comprising a precursor A, a methyl silicone resin film forming agent B, absolute ethyl alcohol, ammonia water and deionized water, wherein the precursor A comprises tetraethoxysilane and methyltriethoxysilane, the molar ratio of the tetraethoxysilane to the methyltriethoxysilane is 100: 60 ~, the molar ratio of the precursor A to the absolute ethyl alcohol to the ammonia water to the deionized water is 1: 30 ~: 2 ~: 5 ~, the addition amount of the methyl silicone resin film forming agent B accounts for 1 ~% of the total mass of the organic-inorganic hybrid hole sealing agent for the coating, the precursor A is mixed with the absolute ethyl alcohol, the ammonia water and the deionized water, and a group containing a silica inorganic component in the hole sealing agent is obtained through a hydrolysis reaction process, the preparation method of the organic-inorganic hybrid hole sealing agent for the plasma sprayed ceramic coating comprises the following steps of (1) mixing the absolute ethyl alcohol, the ammonia water and the deionized water, placing the mixture into a water bath kettle at a temperature of ~ ℃, uniformly stirring, adding the tetraethoxysilane and keeping the mixture for 1h, then placing the hole sealing agent for the plasma sprayed ceramic coating at a constant temperature, and heating to obtain a mixed film forming agent for the plasma sprayed ceramic coating, and adding the triethoxy silane to obtain a mixed film forming agent B, and heating to obtain a temperature of 5970 ℃, and adding the.
2. A preparation method of an organic-inorganic hybrid hole sealing agent for a plasma sprayed ceramic coating is characterized by comprising the following steps:
(1) firstly, mixing absolute ethyl alcohol, ammonia water and deionized water, placing the mixture in a constant-temperature water bath kettle at the temperature of 30 ~ 50 ℃, uniformly stirring, adding tetraethoxysilane, keeping the temperature for 1h, heating to the temperature of 50 ~ 70 ℃, adding methyltriethoxysilane, and placing the mixture at normal temperature to obtain mixed sol, wherein the molar weight ratio of the tetraethoxysilane to the methyltriethoxysilane is 100: 60 ~ 200, the tetraethoxysilane and the methyltriethoxysilane form a precursor A, and the molar weight ratio of the precursor A, the absolute ethyl alcohol, the ammonia water and the deionized water is 1: 30 ~ 35: 2 ~ 3: 5 ~ 7;
(2) and adding the methyl silicone resin film-forming agent B into the mixed sol, and reacting to obtain the organic-inorganic hybrid hole sealing agent for the plasma sprayed ceramic coating.
3. The method for preparing an organic-inorganic hybrid sealing agent for a plasma sprayed ceramic coating according to claim 2, wherein the step (1) is carried out by stirring in a precision-enhanced stirrer.
4. The method for preparing an organic-inorganic hybrid hole sealing agent for plasma spraying ceramic coating according to claim 2, wherein in the step (1), the organic-inorganic hybrid hole sealing agent is placed at normal temperature for 24 hours.
5. The method for preparing the organic-inorganic hybrid hole sealing agent for the plasma spraying ceramic coating according to claim 2, wherein in the step (2), the addition amount of the methyl silicone resin film forming agent B accounts for 1 ~ 5% of the total mass of the organic-inorganic hybrid hole sealing agent for the plasma spraying ceramic coating.
6. The method for preparing an organic-inorganic hybrid hole sealing agent for a plasma sprayed ceramic coating according to claim 2, wherein in the step (2), after reacting for 2 hours, the mixture is kept standing for 48 hours at normal temperature for aging treatment.
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