CN115636692B - High-temperature-resistant and oxidation-resistant ceramic coating and preparation method and application thereof - Google Patents
High-temperature-resistant and oxidation-resistant ceramic coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN115636692B CN115636692B CN202211343195.0A CN202211343195A CN115636692B CN 115636692 B CN115636692 B CN 115636692B CN 202211343195 A CN202211343195 A CN 202211343195A CN 115636692 B CN115636692 B CN 115636692B
- Authority
- CN
- China
- Prior art keywords
- coating
- carbon
- parts
- temperature
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Ceramic Products (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Glass Compositions (AREA)
Abstract
The application belongs to the technical field of composite materials, and discloses a high-temperature-resistant and oxidation-resistant ceramic coating, and a preparation method and application thereof. The ceramic coating comprises a first coating compounded on the surface of the substrate and a second coating compounded on the first coating; the first coating comprises the components: aluminum dihydrogen phosphate, silica sol; the second coating comprises the components: kaolinite, titanium diboride, calcium fluoride, and boron carbide. The ceramic coating of the application takes kaolinite as a main body, has higher high temperature resistance and chemical stability than the traditional coating taking glass phase as a main body or the coating taking aluminum phosphate refractory material as a main body, does not generate rheology and pulverization at high temperature (more than 900 ℃), does not react with water and deicing agent (potassium acetate), is a coating which is more resistant to high temperature, more resistant to oxidation and more waterproof, and has longer service life at high temperature.
Description
Technical Field
The application belongs to the technical field of composite materials, and particularly relates to a high-temperature-resistant and oxidation-resistant ceramic coating, and a preparation method and application thereof.
Background
The carbon/carbon composite material is a composite material which is reinforced by carbon fiber and takes pyrolytic carbon, resin carbon and the like as matrixes, and the material has higher use temperature, higher strength and larger strength under a non-oxidation environmentThe material has low abrasion loss and high energy absorption capacity, and is used as a preferred material of an aircraft brake disc. However, this material has a problem that it is not resistant to oxidation in the atmospheric environment and is significantly oxidized at temperatures above 500 ℃. In use, the aircraft brake disc is required to absorb huge aircraft kinetic energy, so that higher temperature is generated, most conditions can reach 600 ℃ or higher, and few conditions can reach 900 ℃ or higher, so that when no surface protection layer exists, the carbon/carbon composite material is continuously aggravated along with the extension and oxidization of the service time, the material performance and strength are greatly reduced, even the damage and failure of the structure occur, and hidden danger is brought to the safety of the aircraft.
At present, a plurality of oxidation-resistant coating technologies of carbon/carbon composite materials are developed at home and abroad, and the main improvement directions of the oxidation-resistant coating technologies are as follows, wherein one of the oxidation-resistant coating technologies is protected by taking borosilicate glass phase as a main body, and the other oxidation-resistant coating technologies is protected by taking phosphate as a main body, but the oxidation-resistant coating technologies have some defects in actual use: if the aircraft frequently takes off and land and the brake disc is cooled to room temperature and is reused, higher temperature (more than 900 ℃) is generated, and the use requirement of high temperature (more than 900 ℃) is difficult to reach; when the runway is stained with ponding or deicing agent, the water has extremely strong dissolving effect on boron tri-boron generated by boron oxidation or the catalytic effect on the oxidation of carbon/carbon composite materials by potassium ions in the deicing agent, so that the protective effect of the improved coating is greatly reduced, advanced oxidation of the carbon/carbon brake disc still occurs, and the performance and strength of the brake disc are greatly reduced.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the prior art described above. Therefore, the application provides a high-temperature-resistant and oxidation-resistant ceramic coating, and a preparation method and application thereof.
A first aspect of the present application provides a ceramic coating comprising a first coating layer compounded on a surface of a substrate, a second coating layer compounded on the first coating layer; the first coating comprises the components: aluminum dihydrogen phosphate, silica sol; the second coating comprises the components: kaolinite, titanium diboride, calcium fluoride, and boron carbide.
The ceramic coating of the application takes kaolinite as a main body, has higher high temperature resistance and chemical stability than the traditional coating taking glass phase as a main body or the coating taking aluminum phosphate refractory material as a main body, does not generate rheology and pulverization at high temperature (more than 900 ℃), does not react with water and deicing agent (potassium acetate), is a coating which is more resistant to high temperature, more resistant to oxidation and more waterproof, and has longer service life at high temperature.
If the components of the first coating do not contain silica sol, only aluminum dihydrogen phosphate is adopted, after high-temperature treatment, the aluminum dihydrogen phosphate is generated into aluminum phosphate, and the aluminum phosphate has better bonding effect with an oxidation-resistant layer adopting borosilicate glass phase as a main body or adopting phosphate as a main body in the prior art, but the interface bonding effect is general for the second coating adopting kaolinite ceramic layer as a main body. Therefore, the silica sol is added into the first coating, and the silica sol is heated to generate glassy silicon dioxide, so that the vitreous silicon dioxide has better adhesion with the kaolinite ceramic layer, and the vitreous silicon dioxide and the kaolinite ceramic layer have close thermal expansion performance and better durability. Meanwhile, the aluminum phosphate has high temperature resistance, no silica generated by the silica sol after heating is high, the aluminum phosphate can generate a series of decomposition and phase change at the temperature of more than 900 ℃, the material generates a series of performance decay, and the aluminum phosphate matrix is porous and is easy to generate the following problems: firstly, at the temperature of more than 900 ℃, various decomposition reactions of aluminum phosphate are generated, the coating is pulverized, the structure of the coating is changed, particularly, serious pulverization is generated after multiple times of high temperature, the oxidation prevention effect is greatly reduced, and secondly, the waterproof effect is general because of higher porosity of aluminum phosphate, particularly, the waterproof effect is greatly reduced after multiple times of high temperature bearing (after pulverization phenomenon is generated). The silica sol is heated to be more than 800 ℃ to generate glassy silicon dioxide, and the decomposition reaction starts to occur at the temperature of more than 1600 ℃, so that the high temperature resistant effect can be greatly improved by adding the silica sol into the first coating.
The second coating of the application takes kaolinite as a main body to sinter into a ceramic layer, which is an aluminosilicate ceramic, and the main component of the kaolinite is Al 2 O 3 ·2SiO 2 ·2H 2 O, the kaolinite is sintered at high temperature to form white triclinic ceramic, and the ceramic body has the advantages of high temperature resistance (the temperature resistance can reach more than 1500 ℃), good chemical stability (the ceramic body is not decomposed, does not react with oxygen and does not react with water at high temperature), and the like, is a main reason that the ceramic coating of the application is not deformed at high temperature, keeps the form and the performance stable, is a main framework material of the ceramic coating of the application, and plays a decisive role in improving the high temperature resistance of the coating. The Si and Al elements in kaolinite exist in the form of chemical bonds, and the change by heat has two stages, namely a structural dehydration stage and a new crystal formation and conversion stage. At a temperature above 100deg.C, start to disengage adsorptionThe water is heated to 450 ℃ or above, the structural water of the kaolinite is slowly discharged, and the kaolinite becomes metakaolinite in the dehydration process. The metakaolin further reacts to form a silicon-aluminum spinel structure which is a quasi-ceramic phase (layer) by continuing to heat at a temperature above 925 ℃, so that the oxygen diffusion prevention effect is very good at high temperature.
The titanium diboride in the second coating may be combined with kaolinite (aluminosilicate ceramic material) to form a composite ceramic material. The ceramic matrix has higher mechanical strength and fracture toughness by adding titanium diboride, and improves the brittleness of the pure aluminosilicate ceramic. Meanwhile, titanium diboride has better oxidation resistance, and the oxidation resistance temperature in the air can reach 1000 ℃. The titanium diboride is added to inhibit the downward oxidation of a small amount of oxygen penetrating through the ceramic micropores, and the titanium diboride reacts with the oxygen to generate titanium dioxide and diboron trioxide, so that the two materials have the oxidation preventing effect. In addition, the addition of titanium diboride reduces shrinkage during the kaolinite sintering process.
The calcium fluoride in the second coating is mainly used as enamel in the ceramic industry, and can play roles in assisting color and fluxing in the production process of ceramic bodies. Meanwhile, the ceramic coating can form a hydrophobic and airtight glaze layer, can greatly reduce the permeation of oxygen to a substrate, can prevent water and deicing agent from permeating into the coating, and further improves the oxidation resistance and the water resistance of the ceramic layer. In addition, the addition of calcium fluoride can reduce shrinkage during the kaolinite sintering process.
The boron carbide in the second coating is a refractory material with a higher melting point, and is added firstly to improve the heat resistance of the ceramic layer and reduce the structure shrinkage in the sintering process, and secondly to inhibit the downward oxidation effect of a small amount of oxygen penetrating through the micropores of the ceramic layer, at this time, the boron carbide reacts with the oxygen to generate boron trioxide, so that the oxygen is consumed, the boron trioxide capable of preventing further oxidation is generated, and the downward diffusion of the oxygen from the ceramic layer is prevented.
Preferably, the first coating further comprises the components: a coupling agent. The carbon/carbon composite material belongs to a nonpolar material, is not easy to bond, and can improve the bonding stability of aluminum dihydrogen phosphate and the surface of the carbon/carbon composite material by adding a coupling agent.
Preferably, the coupling agent comprises at least one of aluminum triacetylacetonate, methyltrimethoxysilane, methyltriethoxysilane.
Preferably, the second coating further comprises the components: medium temperature glass powder, silica sol and dispersing agent. The addition of the medium-temperature glass frit is to improve the bonding effect of the ceramic layer and the first layer, and simultaneously improve the thermal expansion matching property of the second coating and the first coating, and also has the effect of preventing oxygen penetrating through the ceramic micropores from oxidizing downwards due to the air impermeability of the glass layer. The silica sol is added mainly to further increase the adhesion effect with the first coating. The dispersing agent is added to ensure that all the components can be fully and uniformly mixed, prevent the components from segregation and ensure that a preset structure is sintered.
Preferably, the melting point of the medium temperature glass frit is 800-1100 ℃.
Preferably, the dispersant is an alkoxy dispersant.
Preferably, the dispersant comprises at least one of an alkoxylated polyol, an alkoxypolyamidoamine, an alkoxyphenol ether.
Preferably, the first coating comprises the following components in parts by mass: 15-25 parts of aluminum dihydrogen phosphate and 20-30 parts of silica sol. When the addition amount of the silica sol is too large, the burned first coating layer roughens the surface, has an influence on the brushing of the second coating layer, and the oxidation preventing effect cannot be improved.
Preferably, the first coating further comprises the components in parts by weight: 2-5 parts of coupling agent.
Preferably, the second coating comprises the following components in parts by weight: 20-25 parts of kaolinite, 15-18 parts of titanium diboride, 10-12 parts of calcium fluoride and 5-10 parts of boron carbide. When the addition amount of kaolinite is too low, for example, when the addition amount is less than 20 parts, the high-temperature oxidation preventing effect of the coating is greatly reduced; however, when the addition amount of kaolinite is increased, for example, more than 25 parts, the oxidation preventing effect of the coating layer is not improved any more but the reduction starts to occur, so that the addition amount is further controlled to achieve a preferable oxidation preventing effect.
Preferably, the second coating further comprises the components in parts by weight: 5-8 parts of medium-temperature glass powder, 2-5 parts of silica sol and 1-2 parts of dispersing agent.
Preferably, the ceramic coating has a thickness of 0.04-0.08mm.
The second aspect of the application provides a method for preparing the ceramic coating, which comprises the following steps:
s1, mixing the components of the first coating, coating the mixture on the surface of a substrate, and drying and sintering the mixture to obtain the first coating;
s2, mixing the components of the second coating, coating the mixture on the surface of the first coating, and drying and sintering to obtain the ceramic coating.
According to the application, the first coating is independently sintered, the sintered aluminum dihydrogen phosphate is changed into a cross-linked aluminum phosphate structure, and the silica sol generates glassy silicon dioxide, and the two have eutectic effect, so that the bonding effect and the anti-oxidation effect are improved; if the first coating is not sintered, then only the dried first coating will have a risk of brushing off when the second coating is applied, and the overall oxidation preventing effect of the ceramic coating will be reduced as the first coating does not sinter, cross-link the carbon/carbon composite surface, resulting in a reduced effect of bonding the carbon/carbon composite, the second coating.
Preferably, in step S1, the specific sintering process includes:
under the protection of inert gas, the temperature is raised to 300-350 ℃ at the temperature rising rate of 1-3 ℃/min, and then the temperature is raised to 750-850 ℃ at the temperature rising rate of 3-5 ℃/min.
Preferably, in step S2, the specific sintering process includes:
under the protection of inert gas, the temperature is raised to 330-400 ℃ at the temperature rising rate of 1-3 ℃/min, and then the temperature is raised to 800-950 ℃ at the temperature rising rate of 3-5 ℃/min.
A third aspect of the application provides the use of a ceramic coating according to the application for the preparation of an aerospace component.
A fourth aspect of the present application provides a carbon/carbon composite material comprising a carbon/carbon composite material and a coating layer composited on the carbon/carbon composite material; the coating is the ceramic coating.
Compared with the prior art, the application has the following beneficial effects:
the ceramic coating takes kaolinite as a main body, does not generate rheology and pulverization at high temperature (more than 900 ℃), does not react with water and deicing agent (potassium acetate), is a coating which is more resistant to high temperature, oxidation and water, and has longer service life at high temperature.
The sample formed by the ceramic coating and the carbon/carbon composite material has the oxidation weight loss rate of 4.2-4.8% after being kept at the constant temperature of 1010 ℃ for 2 hours in the air; soaking in 30% potassium acetate solution for 1 hr, taking out, placing in air at 900 deg.C, and maintaining the temperature for 6 hr with oxidation weight loss rate of 6.1-6.6%.
Detailed Description
In order to make the technical solutions of the present application more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the application.
The starting materials, reagents, apparatus used in the examples below were obtained from conventional commercial sources, unless otherwise specified, or may be obtained by methods known in the art.
Example 1
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 15 parts of aluminum dihydrogen phosphate, 20 parts of silica sol, 2 parts of aluminum triacetylacetonate and 63 parts of deionized water; the second coating comprises the components: 20 parts of kaolinite, 18 parts of titanium diboride, 10 parts of calcium fluoride, 10 parts of boron carbide, 5 parts of medium-temperature glass powder, 5 parts of silica sol, 2 parts of dispersing agent and 30 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture for 1 hour at 100 ℃, cooling the mixture, taking the mixture out, placing the mixture in a heat treatment furnace, and introducing nitrogen into the heat treatment furnace for normal-pressure sintering; the specific sintering process is to raise the temperature to 300 ℃ at a heating rate of 3 ℃/min, keep the temperature at 300 ℃ for 1 hour, then raise the temperature to 800 ℃ at a heating rate of 5 ℃/min, and keep the temperature at 800 ℃ for 2 hours; naturally cooling to room temperature (about 25 ℃) along with the furnace, and taking out for standby;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to heat up to 330 ℃ according to the heating rate of 3 ℃/min, heat up to 330 ℃ for 1 hour, then heat up to 930 ℃ according to the heating rate of 5 ℃/min, heat up to 930 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
The carbon/carbon composite material with the ceramic coating prepared in the example is subjected to constant temperature for 24 hours in air at 750 ℃ and has an oxidation weight loss rate of 1.1%.
The carbon/carbon composite material with the ceramic coating prepared in the example is kept at a constant temperature of 1010 ℃ for 2 hours in air, and the oxidation weight loss rate is 4.8%.
The carbon/carbon composite material with the ceramic coating prepared in the embodiment is soaked in 30% potassium acetate solution for 1 hour, taken out and placed in 900 ℃ air, and the constant temperature is kept for 6 hours, and the oxidation weight loss rate is 6.3%.
The carbon/carbon composite material with ceramic coating prepared in this example was subjected to cold and hot alternating air oxidation test at room temperature up to 750 ℃ for 6 hours at 750 ℃ for 4 times, and the oxidation weight loss rate was 1.2%.
Example 2
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 25 parts of aluminum dihydrogen phosphate, 30 parts of silica sol, 5 parts of aluminum triacetylacetonate and 40 parts of deionized water; the second coating comprises the components: 22 parts of kaolinite, 15 parts of titanium diboride, 12 parts of calcium fluoride, 8 parts of boron carbide, 8 parts of medium-temperature glass powder, 2 parts of silica sol, 1 part of dispersing agent and 32 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture for 1 hour at 100 ℃, cooling the mixture, taking the mixture out, placing the mixture in a heat treatment furnace, and introducing nitrogen into the heat treatment furnace for normal-pressure sintering; the specific sintering process is to raise the temperature to 350 ℃ at the heating rate of 3 ℃/min, keep the temperature at 350 ℃ for 1 hour, then raise the temperature to 850 ℃ at the heating rate of 5 ℃/min, and keep the temperature at 850 ℃ for 2 hours; naturally cooling to room temperature along with the furnace, and taking out for standby;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to raise the temperature to 400 ℃ according to the heating rate of 3 ℃/min, keep the temperature at 400 ℃ for 1 hour, then raise the temperature to 950 ℃ according to the heating rate of 5 ℃/min, and keep the temperature at 950 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
The carbon/carbon composite material with the ceramic coating prepared in the example is subjected to constant temperature for 24 hours in air at 750 ℃ and has an oxidation weight loss rate of 1.3%.
The carbon/carbon composite material with the ceramic coating prepared in the example is kept at a constant temperature of 1010 ℃ for 2 hours in air, and the oxidation weight loss rate is 4.5%.
The carbon/carbon composite material with the ceramic coating prepared in the embodiment is soaked in 30% potassium acetate solution for 1 hour, taken out and placed in 900 ℃ air, and the constant temperature is kept for 6 hours, and the oxidation weight loss rate is 6.1%.
Example 3
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 20 parts of aluminum dihydrogen phosphate, 25 parts of silica sol, 3 parts of aluminum triacetylacetonate and 52 parts of deionized water; the second coating comprises the components: 25 parts of kaolinite, 18 parts of titanium diboride, 10 parts of calcium fluoride, 5 parts of boron carbide, 5 parts of medium-temperature glass powder, 5 parts of silica sol, 2 parts of dispersing agent and 30 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture for 1 hour at 100 ℃, cooling the mixture, taking the mixture out, placing the mixture in a heat treatment furnace, and introducing nitrogen into the heat treatment furnace for normal-pressure sintering; the specific sintering process is to raise the temperature to 300 ℃ at a heating rate of 1 ℃/min, keep the temperature at 300 ℃ for 1 hour, then raise the temperature to 750 ℃ at a heating rate of 3 ℃/min, and keep the temperature at 750 ℃ for 2 hours; naturally cooling to room temperature along with the furnace, and taking out for standby;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to heat up to 330 ℃ according to the heating rate of 1 ℃/min, heat up to 330 ℃ for 1 hour, then heat up to 800 ℃ according to the heating rate of 3 ℃/min, and heat up to 800 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
The carbon/carbon composite material with the ceramic coating prepared in the example is subjected to constant temperature for 24 hours in air at 750 ℃ and has an oxidation weight loss rate of 1.6%.
The carbon/carbon composite material with the ceramic coating prepared in the example is kept at a constant temperature of 1010 ℃ for 2 hours in air, and the oxidation weight loss rate is 4.2%.
The carbon/carbon composite material with the ceramic coating prepared in the embodiment is soaked in 30% potassium acetate solution for 1 hour, taken out and placed in 900 ℃ air, and the constant temperature is kept for 6 hours, and the oxidation weight loss rate is 6.6%.
Example 4
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 15 parts of aluminum dihydrogen phosphate, 20 parts of silica sol, 2 parts of aluminum triacetylacetonate and 63 parts of deionized water; the second coating comprises the components: 30 parts of kaolinite, 18 parts of titanium diboride, 10 parts of calcium fluoride, 10 parts of boron carbide, 5 parts of medium-temperature glass powder, 5 parts of silica sol, 2 parts of dispersing agent and 20 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture for 1 hour at 100 ℃, cooling the mixture, taking the mixture out, placing the mixture in a heat treatment furnace, and introducing nitrogen into the heat treatment furnace for normal-pressure sintering; the specific sintering process is to raise the temperature to 300 ℃ at a heating rate of 3 ℃/min, keep the temperature at 300 ℃ for 1 hour, then raise the temperature to 800 ℃ at a heating rate of 5 ℃/min, and keep the temperature at 800 ℃ for 2 hours; naturally cooling to room temperature (about 25 ℃) along with the furnace, and taking out for standby;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to heat up to 330 ℃ according to the heating rate of 3 ℃/min, heat up to 330 ℃ for 1 hour, then heat up to 930 ℃ according to the heating rate of 5 ℃/min, heat up to 930 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
The carbon/carbon composite material with the ceramic coating prepared in the example is kept at a constant temperature of 1010 ℃ for 2 hours in air, and the oxidation weight loss rate is 6.7%.
The carbon/carbon composite material with the ceramic coating prepared in the embodiment is soaked in 30% potassium acetate solution for 1 hour, taken out and placed in 900 ℃ air, and the constant temperature is maintained for 6 hours, wherein the oxidation weight loss rate is 9.6%.
Example 5
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 15 parts of aluminum dihydrogen phosphate, 20 parts of silica sol, 2 parts of aluminum triacetylacetonate and 63 parts of deionized water; the second coating comprises the components: 20 parts of kaolinite, 18 parts of titanium diboride, 10 parts of calcium fluoride, 10 parts of boron carbide, 5 parts of medium-temperature glass powder, 5 parts of silica sol, 2 parts of dispersing agent and 30 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture at 100 ℃ for 1 hour, cooling the mixture, and taking the mixture out for later use;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to heat up to 330 ℃ according to the heating rate of 3 ℃/min, heat up to 330 ℃ for 1 hour, then heat up to 930 ℃ according to the heating rate of 5 ℃/min, heat up to 930 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
The carbon/carbon composite material with the ceramic coating prepared in the example is kept at a constant temperature of 1010 ℃ for 2 hours in air, and the oxidation weight loss rate is 8.3%.
The carbon/carbon composite material with the ceramic coating prepared in the embodiment is soaked in 30% potassium acetate solution for 1 hour, taken out and placed in 900 ℃ air, and the constant temperature is kept for 6 hours, and the oxidation weight loss rate is 10.8%.
Comparative example 1 (the difference from example 1 is that the components of the first coating of comparative example 1 do not contain silica sol)
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 15 parts of aluminum dihydrogen phosphate, 2 parts of aluminum triacetylacetonate and 83 parts of deionized water; the second coating comprises the components: 20 parts of kaolinite, 18 parts of titanium diboride, 10 parts of calcium fluoride, 10 parts of boron carbide, 5 parts of medium-temperature glass powder, 5 parts of silica sol, 2 parts of dispersing agent and 30 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture for 1 hour at 100 ℃, cooling the mixture, taking the mixture out, placing the mixture in a heat treatment furnace, and introducing nitrogen into the heat treatment furnace for normal-pressure sintering; the specific sintering process is to raise the temperature to 300 ℃ at a heating rate of 3 ℃/min, keep the temperature at 300 ℃ for 1 hour, then raise the temperature to 800 ℃ at a heating rate of 5 ℃/min, and keep the temperature at 800 ℃ for 2 hours; naturally cooling to room temperature (about 25 ℃) along with the furnace, and taking out for standby;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to heat up to 330 ℃ according to the heating rate of 3 ℃/min, heat up to 330 ℃ for 1 hour, then heat up to 930 ℃ according to the heating rate of 5 ℃/min, heat up to 930 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
After the carbon/carbon composite material with the ceramic coating layer prepared in this comparative example was subjected to a cold and hot alternating air oxidation test in which the room temperature was raised to 750 ℃ for 6 hours at 750 ℃, the oxidation weight loss rate was 3.2%, and cracks were formed in the coating layer. From this, it can be seen that the cold and hot cycle durability of the coating and the temperature resistance of the overall oxidation preventing coating were significantly reduced when the component of the first coating in comparative example 1 was free of silica sol, as compared with example 1.
Comparative example 2 (the difference from example 1 is that the component kaolinite of the second coating of comparative example 2 is replaced by SiO 2 And Al 2 O 3 )
A ceramic coating, comprising a first coating layer compounded on the surface of a carbon/carbon composite material and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by weight: 15 parts of aluminum dihydrogen phosphate, 20 parts of silica sol, 2 parts of aluminum triacetylacetonate and 63 parts of deionized water; the second coating comprises the components: siO (SiO) 2 11 parts of Al 2 O 3 9 parts of titanium diboride, 18 parts of calcium fluoride, 10 parts of boron carbide, 5 parts of medium-temperature glass powder, 5 parts of silica sol, 2 parts of dispersing agent and 30 parts of deionized water.
A method for preparing a carbon/carbon composite material having a ceramic coating, comprising the steps of:
s1, pretreatment: washing the carbon/carbon composite material with deionized water, then placing the carbon/carbon composite material in an oven, drying the carbon/carbon composite material for 2 hours at 110 ℃, cooling the carbon/carbon composite material, and taking the carbon/carbon composite material out for later use;
s2, preparing a first coating: uniformly mixing the components of the first coating, brushing the mixture to the surface of the pretreated carbon/carbon composite material, then placing the mixture in an oven, drying the mixture for 1 hour at 100 ℃, cooling the mixture, taking the mixture out, placing the mixture in a heat treatment furnace, and introducing nitrogen into the heat treatment furnace for normal-pressure sintering; the specific sintering process is to raise the temperature to 300 ℃ at a heating rate of 3 ℃/min, keep the temperature at 300 ℃ for 1 hour, then raise the temperature to 800 ℃ at a heating rate of 5 ℃/min, and keep the temperature at 800 ℃ for 2 hours; naturally cooling to room temperature (about 25 ℃) along with the furnace, and taking out for standby;
s3, preparing a second coating: uniformly mixing the components of the second coating, brushing the mixture to the surface of the first coating, placing the first coating in an oven, drying the first coating at 100 ℃ for 1 hour, cooling the first coating, taking the second coating out, placing the second coating in a heat treatment furnace, and introducing nitrogen for normal-pressure sintering; the specific sintering process is to heat up to 330 ℃ according to the heating rate of 3 ℃/min, heat up to 330 ℃ for 1 hour, then heat up to 930 ℃ according to the heating rate of 5 ℃/min, heat up to 930 ℃ for 2 hours; and naturally cooling to room temperature along with the furnace, and taking out to obtain the carbon/carbon composite material with the ceramic coating.
The carbon/carbon composite material with the ceramic coating prepared in the comparative example is soaked in 30% potassium acetate solution for 1 hour, taken out and placed in 900 ℃ air, the constant temperature is maintained for 6 hours, the oxidation weight loss rate is 14.5%, and the coating has pulverization phenomenon. From this, it can be seen that the oxidation resistance of comparative example 1 is significantly lowered as compared with example 1. The reason may be due to SiO 2 And Al 2 O 3 At a sintering temperature of 800-1000 ℃, the eutectic cristobalite-mullite phase (layer) cannot be generated, siO 2 And Al 2 O 3 Only in the coating layer in the form of the respective simple substance, i.e. a continuous closed eutectic phase (layer) cannot be formed, the oxygen diffusion preventing effect thereof will be reduced.
While the preferred embodiment of the present application has been described in detail, the application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the application, and these modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (8)
1. A ceramic coating, which is characterized by comprising a first coating layer compounded on the surface of a substrate and a second coating layer compounded on the first coating layer; the first coating comprises the following components in parts by mass: 15-25 parts of aluminum dihydrogen phosphate and 20-30 parts of silica sol; the second coating comprises the components: 20-25 parts of kaolinite, 15-18 parts of titanium diboride, 10-12 parts of calcium fluoride and 5-10 parts of boron carbide.
2. The ceramic coating of claim 1, wherein the first coating further comprises the components: a coupling agent.
3. The ceramic coating of claim 1, wherein the second coating further comprises the components: medium temperature glass powder, silica sol and dispersing agent.
4. A method for producing a ceramic coating according to any one of claims 1 to 3, comprising the steps of:
s1, mixing the components of the first coating, coating the mixture on the surface of a substrate, and drying and sintering the mixture to obtain the first coating;
s2, mixing the components of the second coating, coating the mixture on the surface of the first coating, and drying and sintering to obtain the ceramic coating.
5. The method according to claim 4, wherein in step S1, the specific sintering process comprises:
under the protection of inert gas, the temperature is raised to 300-350 ℃ at the temperature rising rate of 1-3 ℃/min, and then the temperature is raised to 750-850 ℃ at the temperature rising rate of 3-5 ℃/min.
6. The method according to claim 4, wherein in step S2, the specific sintering process includes:
under the protection of inert gas, the temperature is raised to 330-400 ℃ at the temperature rising rate of 1-3 ℃/min, and then the temperature is raised to 800-950 ℃ at the temperature rising rate of 3-5 ℃/min.
7. Use of a ceramic coating according to any one of claims 1-3 for the preparation of an aerospace component.
8. A carbon/carbon composite material comprising a carbon/carbon composite material and a coating layer composited on the carbon/carbon composite material; the coating is a ceramic coating according to any one of claims 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211343195.0A CN115636692B (en) | 2022-10-31 | 2022-10-31 | High-temperature-resistant and oxidation-resistant ceramic coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211343195.0A CN115636692B (en) | 2022-10-31 | 2022-10-31 | High-temperature-resistant and oxidation-resistant ceramic coating and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115636692A CN115636692A (en) | 2023-01-24 |
| CN115636692B true CN115636692B (en) | 2023-08-29 |
Family
ID=84947433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211343195.0A Active CN115636692B (en) | 2022-10-31 | 2022-10-31 | High-temperature-resistant and oxidation-resistant ceramic coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115636692B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023157B (en) * | 2023-02-14 | 2023-09-19 | 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) | Environment-friendly fireproof high-temperature-resistant graphite material coating and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318835A (en) * | 2008-07-17 | 2008-12-10 | 孙文革 | Oxidation protection processing method for carbon/carbon composite material aviation brake piece |
| CN101328077A (en) * | 2008-07-17 | 2008-12-24 | 居小平 | Oxidation protection air blocking layer coating of carbon/carbon composite material aviation brake part |
| CN103740284A (en) * | 2014-01-06 | 2014-04-23 | 武汉双虎涂料有限公司 | High temperature-resistant composite inorganic binder, as well as preparation method and application thereof |
| CN105198492A (en) * | 2015-09-25 | 2015-12-30 | 东南大学 | Oxidation-resistant coating and preparation method thereof |
| CN105646007A (en) * | 2014-12-02 | 2016-06-08 | 中国科学院金属研究所 | Preparation method of low-temperature long-time oxidation-resistant coating layer on carbon/carbon composite material surfaces |
| CN105793390A (en) * | 2013-12-06 | 2016-07-20 | 堺化学工业株式会社 | Stress-induced light-emission material, method for manufacturing stress-induced light-emission material, stress-induced light-emission paint composition, resin composition, and stress-induced light-emission body |
| CN108148532A (en) * | 2018-02-06 | 2018-06-12 | 黑龙江省科学院石油化学研究院 | A kind of normal temperature cure organic-inorganic composite high-temperature Resistance Adhesives and preparation method thereof |
| CN109704810A (en) * | 2018-12-21 | 2019-05-03 | 北京隆源纳欣科技有限公司 | A kind of inorganic high-temperature resistant ceramic wear-resisting anticorrosive paint |
| CN111362727A (en) * | 2020-03-18 | 2020-07-03 | 德翼高科(杭州)科技有限公司 | Phosphate anti-oxidation coating of carbon/carbon composite material and coating process thereof |
| CN111825476A (en) * | 2020-07-24 | 2020-10-27 | 江西宁新新材料股份有限公司 | Graphite high-temperature antioxidant capable of being rapidly dried at normal temperature and application thereof |
| CN113004029A (en) * | 2021-04-08 | 2021-06-22 | 北京理工大学 | High-temperature-resistant ceramic coating with double-layer structure and preparation method and application thereof |
| CN113716977A (en) * | 2021-06-10 | 2021-11-30 | 西北工业大学 | Wide-temperature-range composite anti-oxidation coating on surface of carbon/carbon composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6668984B2 (en) * | 2000-12-06 | 2003-12-30 | Honeywell Advanced Composites Inc. | Oxidation protection for carbon/carbon composite and graphite friction materials |
| WO2008098421A1 (en) * | 2007-02-15 | 2008-08-21 | Institute Of Process Engineering, Chinese Academy Of Sciences | High temperature resistant inorganic composite adhesive |
-
2022
- 2022-10-31 CN CN202211343195.0A patent/CN115636692B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318835A (en) * | 2008-07-17 | 2008-12-10 | 孙文革 | Oxidation protection processing method for carbon/carbon composite material aviation brake piece |
| CN101328077A (en) * | 2008-07-17 | 2008-12-24 | 居小平 | Oxidation protection air blocking layer coating of carbon/carbon composite material aviation brake part |
| CN105793390A (en) * | 2013-12-06 | 2016-07-20 | 堺化学工业株式会社 | Stress-induced light-emission material, method for manufacturing stress-induced light-emission material, stress-induced light-emission paint composition, resin composition, and stress-induced light-emission body |
| CN103740284A (en) * | 2014-01-06 | 2014-04-23 | 武汉双虎涂料有限公司 | High temperature-resistant composite inorganic binder, as well as preparation method and application thereof |
| CN105646007A (en) * | 2014-12-02 | 2016-06-08 | 中国科学院金属研究所 | Preparation method of low-temperature long-time oxidation-resistant coating layer on carbon/carbon composite material surfaces |
| CN105198492A (en) * | 2015-09-25 | 2015-12-30 | 东南大学 | Oxidation-resistant coating and preparation method thereof |
| CN108148532A (en) * | 2018-02-06 | 2018-06-12 | 黑龙江省科学院石油化学研究院 | A kind of normal temperature cure organic-inorganic composite high-temperature Resistance Adhesives and preparation method thereof |
| CN109704810A (en) * | 2018-12-21 | 2019-05-03 | 北京隆源纳欣科技有限公司 | A kind of inorganic high-temperature resistant ceramic wear-resisting anticorrosive paint |
| CN111362727A (en) * | 2020-03-18 | 2020-07-03 | 德翼高科(杭州)科技有限公司 | Phosphate anti-oxidation coating of carbon/carbon composite material and coating process thereof |
| CN111825476A (en) * | 2020-07-24 | 2020-10-27 | 江西宁新新材料股份有限公司 | Graphite high-temperature antioxidant capable of being rapidly dried at normal temperature and application thereof |
| CN113004029A (en) * | 2021-04-08 | 2021-06-22 | 北京理工大学 | High-temperature-resistant ceramic coating with double-layer structure and preparation method and application thereof |
| CN113716977A (en) * | 2021-06-10 | 2021-11-30 | 西北工业大学 | Wide-temperature-range composite anti-oxidation coating on surface of carbon/carbon composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115636692A (en) | 2023-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104671815B (en) | ZrC-TiC modified C/C-SiC composite material and preparation method thereof | |
| CN104230367B (en) | A kind of SiC-ZrC-ZrB 2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof | |
| CN115636692B (en) | High-temperature-resistant and oxidation-resistant ceramic coating and preparation method and application thereof | |
| CN112374917B (en) | High-temperature ceramic coating and preparation method thereof | |
| CN103265331B (en) | C/SiC/Na2SiO3 antioxidative compound coating suitable for graphite material and preparation method thereof | |
| CN113480308B (en) | High-temperature-resistant ablation-resistant low-temperature chemically bonded phosphate group ceramizable material and preparation method thereof | |
| CN114315390B (en) | Carbon/carbon composite material surface wide-temperature-range long-life antioxidation coating and low-temperature preparation method | |
| CN106587629A (en) | Boride modified glass ceramic based composite high-temperature oxidation resisting coating and preparation method thereof | |
| CN113563113A (en) | High-temperature oxidation-resistant coating on surface of carbon-based composite material and preparation method thereof | |
| CN112279685A (en) | MTaO with environmental thermal barrier coating4Graphite-based composite material and preparation method thereof | |
| CN102492318B (en) | Carbon/carbon composite material anti-oxidizing agent and thermal treatment method | |
| RU2471751C1 (en) | Method of producing protective coating and composition of protective coating mixture | |
| CN101081745A (en) | Carbon/carbon composite material dissolvent thermal modification method | |
| CN111233498A (en) | Environmental barrier coating and preparation method and application thereof | |
| CN116621593A (en) | Low-density C/C composite SiB 6 Preparation method of Glass antioxidant coating | |
| CN114956845A (en) | Preparation method of wide-temperature-range self-healing modified ceramic matrix composite material | |
| KR20040069837A (en) | Method for Making Oxidation Protective Double Coating for Carbon/Carbon Composite | |
| WO1998046539A1 (en) | High-radiation glass base covering material, high-radiation glass film, and process for the production of high-radiation glass film | |
| CN112142499A (en) | Preparation of SiO on the surface of carbon/carbon composite material2Method for preparing microporous anti-oxidation coating with-SiC mosaic structure | |
| CN102503585A (en) | Method for preparing carbon/carbon composite antioxidant phosphate rare-earth glass coating | |
| KR100520435B1 (en) | Method for Making Oxidation Protective Coating for Carbon/Carbon Composite | |
| CN112430130B (en) | High-temperature-resistant composite coating and preparation process thereof | |
| CN117964364B (en) | High-entropy rare earth silicate complex-phase ceramic and preparation method thereof | |
| CN114606493B (en) | NbB-containing alloy for niobium alloy 2 /Nb 3 B 2 Antioxidant coating of composite diffusion barrier and preparation method thereof | |
| CN117125999A (en) | Antioxidant coating applicable to carbon-ceramic composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |