CN108610960B - Ceramic surface material and surface coating - Google Patents
Ceramic surface material and surface coating Download PDFInfo
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Abstract
The present invention provides a ceramic surface material comprising: 20.0-70.0 wt% of organic silicon, 20.0-70.0 wt% of organic solvent, 1.0-50 wt% of filler and 0.1-3.0 wt% of auxiliary agent, wherein the organic solvent is selected from one or more of butyl acetate, dimethylbenzene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate; the filler is composed of graphene, graphite, transition metal oxides, composite silicates, rare earth oxides, nonmetal compounds, transition metal borides, whiskers and metals. The components of the ceramic surface material described above work synergistically with each other to provide better overall performance as a coating.
Description
Technical Field
The invention relates to the technical field of surface materials, in particular to a ceramic surface material and a surface coating.
Background
In the production and operation of aviation, spacecraft, power station boilers, biomass boilers, waste incineration boilers, petrochemical heating furnaces, medium and small industrial boilers, various engines and other thermal equipment, the high-temperature corrosion, erosion wear, contamination, slagging and the like of a heating surface cause great hidden dangers to the safe operation of the equipment, and meanwhile, the heat exchange efficiency and the heat exchange capacity of the equipment can be influenced. The direct damage of a heating surface is caused by high-temperature corrosion and erosion abrasion, the contamination and slagging of the heat exchange surface directly cause the reduction of heat exchange capability, the unbalance of a thermodynamic system of thermodynamic equipment and the reduction of heat efficiency, and simultaneously the problems of furnace tube overtemperature operation, generation of nitric oxides, aggravation of emission, overhigh smoke exhaust temperature and the like caused by the rise of the temperature of a hearth; and the contamination and slagging can also aggravate the corrosion of the heat exchange surface. The problems directly affect the safe production, energy conservation and emission reduction, the product quality and the productivity, the service life of the equipment is reduced, and huge loss is brought to enterprises.
Aiming at the problems of high-temperature corrosion, fouling, slagging and erosion abrasion, the traditional solution is to optimize the design and the operation, improve the grade of the base material of the heat exchange surface, apply metal thermal spraying and build-up welding to deposit silicate ceramic surface materials and organosilicon ceramic surface materials, but the method does not fundamentally solve the problems of high-temperature corrosion, erosion abrasion and fouling slagging and potential safety hazards still exist.
The surface material is an important engineering material, and is a liquid or solid material which can form a film under a certain condition after being coated on the surface of an object and has special functions of protection, decoration, insulation, corrosion prevention, shock resistance, heat resistance and the like. The composite organic silicon high-temperature corrosion resistant self-healing ceramic surface material is a novel environment-friendly functional material, has the advantages of high temperature resistance, wide applicable temperature range, corrosion resistance, high hardness, high weather resistance, non-adhesion and the like, and is an ideal surface material.
In order to solve the problems of high-temperature corrosion, erosion wear and contamination and slagging in the production operation of boilers and the like, researchers develop a series of high-temperature-resistant and slagging-resistant silicate ceramic materials, and in order to strengthen the stability of the boilers in the production process, the researchers further strengthen the performance of ceramic surface materials at the same time so as to obtain the ceramic surface materials with better comprehensive performance, thereby ensuring that heating equipment such as boilers and the like in the industry can stably operate. For example: chinese patent application No. 201410687121.8 discloses a high temperature resistant, stain resistant, and slag bonded ceramic surfacing material comprising: a filler comprising zirconia, silicon nitride, silicon carbide, titania, kaolin and rare earth oxides, a binder and water, which provides a ceramic surface material that is resistant to temperatures of 1050 c, but which is still not very high in its overall properties, particularly resistance to sulfur and chlorine corrosion in a reducing atmosphere. Chinese patent application No. 201510542509.3 discloses a high temperature corrosion resistant stain resistant slagging ceramic surface material comprising: the self-healing ceramic surface material is characterized by comprising a filler, a binder and water, wherein the filler comprises graphite, boron nitride and rare earth oxide, the ceramic surface material provided by the patent can resist the high temperature of 850 ℃, but the comprehensive performance, particularly the high temperature resistance, of the surface material can not meet the requirement of a high-temperature environment, the existing patent of the organosilicon high-temperature corrosion-resistant surface material generally has the defects that the porosity of a ceramic layer is higher and a through crack exists in the process of heating and pyrolyzing the organosilicon, and the adopted self-healing filler substances are mostly alkali metal glass, metal oxide, non-metal compounds with higher melting point temperature and the like, so that the self-healing ceramic surface material has lower self-healing capability in the widest temperature range (250-800 ℃) for industrial application and can not well resist chlorine corrosion and reducing sulfur corrosion, and a corrosion medium penetrates through the.
Disclosure of Invention
The invention aims to provide a ceramic surface material with better comprehensive performance, which is particularly characterized in that the ceramic surface material has better corrosion resistance, high temperature resistance and self-healing capability.
In view of the above, the present application provides a ceramic surface material, which is composed of the following components:
the organic solvent is selected from one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate;
the filler is composed of graphene, graphite, transition metal oxides, composite silicates, rare earth oxides, nonmetal compounds, transition metal borides, whiskers and metals.
Preferably, the silicone is selected from one or more of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, polysilocarbazane and polyborazane.
Preferably, the transition group metal oxide is selected from one or more of zirconia, chromia, titania, molybdenum oxide and niobium oxide; the metal is selected from one or more of chromium, nickel, titanium, aluminum and yttrium; the composite silicate is selected from one or more of copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate; the rare earth oxide is selected from one or more of cerium oxide, yttrium oxide and lanthanum oxide; the nonmetal is selected from one or two of silicon and boron; the non-metallic compound is selected from one or more of boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide; the transition metal boride is selected from one or more of titanium boride, zirconium boride, chromium boride and nickel boride; the whisker is selected from one or two of silicon carbide whisker and silicon nitride whisker; the auxiliary agent is selected from one or more of silane coupling agent, wetting dispersant and catalytic curing agent.
Preferably, the particle size of the filler is 50-900 nm.
Preferably, when the organic silicon is one or more of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, polysilocarbane and polyborazane, the content of the polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilocarbane and polysilocarbazane is independently 0.5 to 70 wt%.
Preferably, when the organosilicon is polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, polysilocarbane, and a mixture of polysiloxazanes, the content of the polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilocarbane, and polysilocarbzanes is independently 0.5 to 67 wt%.
Preferably, when the organosilicon is polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, a mixture of polysilazane and polyborazane, the content of the organosilicon is 30 to 60 wt%, the content of the polysilazane is 10 to 20 wt%, and the content of the polysiloxane, polysilazane, polysiloxazane and polyborazane is independently 2 to 5 wt%.
Preferably, when the organic solvent is one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate, the content of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate is independently 0.5 to 70 wt%.
Preferably, when the organic solvent is a mixture of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate, the content of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate is independently 0.5 to 67 wt%.
Preferably, when the rare earth oxide is cerium oxide, yttrium oxide and lanthanum oxide, the content of cerium oxide, yttrium oxide and lanthanum oxide is independently 0.1 wt% to 2 wt%;
the content of the graphite is 0.1 to 3 weight percent; the content of the graphene is 0.1-3 wt%;
when the metal is chromium, nickel, titanium, aluminum and yttrium, the content of chromium, nickel, titanium, aluminum and yttrium is independently 0.1 wt% -20 wt%;
when the composite silicate is copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate, the content of the copper chromium spinel, the magnesium aluminate spinel, the mullite, the nepheline, the kaolin, the kyanite, the aluminum silicate and the zirconium silicate is independently 0.1-20 wt%;
when the nonmetal is silicon and boron, the content of the silicon and the boron is independently 0.1 wt% -20 wt%;
when the non-metallic compound is boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide, the content of the boron carbide, the silicon boride, the boron nitride, the silicon carbide and the boron oxide is independently 0.1-20 wt%;
when the transition metal boride is titanium boride, zirconium boride, chromium boride and nickel boride, the content of the titanium boride, the content of the zirconium boride, the content of the chromium boride and the content of the nickel boride are independently 0.1 to 20 weight percent;
when the whiskers are silicon carbide whiskers and silicon nitride whiskers, the content of the silicon carbide whiskers and the content of the silicon nitride whiskers are independently 0.1-5 wt%;
when the transition metal oxide is zirconia, chromia, titania, molybdenum oxide, and niobium oxide, the zirconia, chromia, titania, molybdenum oxide, and niobium oxide are independently contained in an amount of 0.1 wt% to 20 wt%.
Preferably, when the rare earth oxide is cerium oxide, yttrium oxide and lanthanum oxide, the content of cerium oxide, yttrium oxide and lanthanum oxide is independently 0.3 wt% to 1.5 wt%;
the content of the graphite is 0.2 wt% -2 wt%; the content of the graphene is 0.2 wt% -2 wt%;
when the metal is chromium, nickel, titanium, aluminum and yttrium, the content of chromium, nickel, titanium, aluminum and yttrium is independently 0.2 wt% -3 wt%;
when the nonmetal is silicon and boron, the content of the silicon and the boron is independently 0.2 to 3 weight percent;
when the composite silicate is copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate, the content of the copper chromium spinel, the magnesium aluminate spinel, the mullite, the nepheline, the kaolin, the kyanite, the aluminum silicate and the zirconium silicate is independently 0.2 to 3 weight percent;
when the non-metallic compound is boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide, the content of the boron carbide, the silicon boride, the boron nitride, the silicon carbide and the boron oxide is independently 0.2-3 wt%;
when the transition metal boride is titanium boride, zirconium boride, chromium boride and nickel boride, the content of the titanium boride, the content of the zirconium boride, the content of the chromium boride and the content of the nickel boride are independently 0.2 to 3 weight percent;
when the whiskers are silicon carbide whiskers and silicon nitride whiskers, the content of the silicon carbide whiskers and the content of the silicon nitride whiskers are independently 0.2 wt% -2 wt%;
when the transition metal oxide is zirconia, chromia, titania, molybdenum oxide, and niobium oxide, the contents of the zirconia, chromia, titania, molybdenum oxide, and niobium oxide are independently 0.2 wt% to 3 wt%.
The application also provides a surface coating, which comprises a surface layer coating and a primer, wherein the surface layer coating is the ceramic surface material.
The present application provides a ceramic surface material comprising: 20.0-70.0 wt% of organic silicon, 20.0-70.0 wt% of organic solvent, 1.0-50 wt% of filler and 0.1-3.0 wt% of auxiliary agent, wherein the organic solvent is selected from one or more of butyl acetate, dimethylbenzene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate; the filler is composed of graphene, graphite, transition metal oxides, composite silicates, rare earth oxides, nonmetals, nonmetallic compounds, transition metal borides, whiskers and metals. The utility model provides an organosilicon among the ceramic surface material forms the compound ceramic material structure of space netted nitrogen carbon borosilicate after releasing gas such as carbon dioxide, methane through pyrolytic reaction under first intensification and high temperature state, and react with other inorganic component and form covalent bond and ceramic-ization, simultaneously rare earth oxide in the filler is favorable to the grain refinement, it forms the network to fill the crystalline grain clearance, compound silicate and filler such as metal interact under high temperature form the melting softening and even flow state compound ceramic component, can fill in the hole that the gas produced by organosilicon pyrolytic cracking produces and destroy the crackle that produces automatically, thereby improve ceramic surface material's high temperature and normal atmospheric temperature's toughness, thermal stability, high temperature corrosion resistance and thermodynamic characteristics etc.. In summary, the above components in the present application act synergistically to provide ceramic surface materials with good properties, such as: high temperature resistance, high heat exchange performance, corrosion resistance, abrasion resistance, high emissivity, contamination and slag bonding resistance and self-healing capability.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problem of poor comprehensive performance of the ceramic surface material in the prior art, the embodiment of the invention discloses the ceramic surface material, wherein a synergistic system is formed by an organic solvent, a filler, an auxiliary agent and organic silicon in the ceramic surface material, and the ceramic layer has high comprehensive performance of oxidation resistance, corrosion resistance, wear resistance, self-cleaning, high toughness, higher thermal conductivity and emissivity and excellent self-repairing and self-healing capabilities according to the specific requirements of different use environments. Specifically, the application provides a ceramic surface material, which consists of the following components:
the organic solvent is selected from one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate;
the filler is composed of graphene, graphite, transition metal oxides, composite silicates, rare earth oxides, nonmetals, nonmetallic compounds, transition metal borides, whiskers and metals.
In the present application, the silicone is selected from one or more of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, polysilacarbozane, and polyborazane; in particular embodiments, the silicone is a polysilazane, a polysilaborazane, a polysiloxane, a polysiloxazane, a polysilazane, a polysilocarbazane, and a mixture of polyborazanes. The organic silicon is used as a basic component of the surface ceramic coating and is used as a bridge to act together with other components; specifically, after gases such as carbon dioxide and methane are released through pyrolysis reaction under the first temperature rise and high temperature state, the organic silicon forms a space net-shaped nitrogen-carbon-boron-silicon composite ceramic material structure, and reacts with other inorganic components to form covalent bonds and ceramic.
In the present application, when the silicone is one or more of polysilazane, polyborosilazane, polysiloxane, polysiloxazane, polysilazane, polysilocarbazane, and polyborosilazane, the content of the polysilazane, polyborosilazane, polysiloxane, polysiloxazane, and polysilocarbazane is independently 0.5 to 70 wt%; when the organosilicon is polysilazane, polyborosilazane, polysiloxane, polysiloxazane, polysilazane, polysilocarbane, and a mixture of polysiloxazanes, the content of the polysilazane, the polysiloborazane, polysiloxane, polysiloxazane, polysilocarbane, and polysilocarbazane is independently 0.5-67 wt%. In a specific embodiment, the content of the silicone is 30 to 60 wt%, in which case the content of the polysilazane is 10 to 20 wt%, the content of the polysilaborazane is 10 to 20 wt%, and the contents of the polysiloxane, the polysilazane, the polysilacarbozane, and the polyborazane are independently 2 to 5 wt%. If the content of the organic silicon exceeds the range, a space network structure cannot be effectively formed, so that the space stability of the nitrogen-carbon-boron-silicon composite ceramic material structure can be reduced, the ceramic surface is insufficiently or excessively sufficiently ceramized, and the self-healing capability and the corrosion resistance of the ceramic surface material are directly influenced.
The solvent of the ceramic surface material is an organic solvent, and the organic solvent is selected from one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate; in specific embodiments, the organic solvent is butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate. The content of the organic solvent is 20 wt% to 70 wt%, and in a specific embodiment, the content of the organic solvent is 30 wt% to 60 wt%. Specifically, when the organic solvent is one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate, the content of the butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate is independently 0.5 wt% to 70 wt%; when the organic solvent is a mixture of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate, the content of the butyl acetate, the xylene, the n-butyl ether, the diethylene glycol butyl ether acetate, the methylcyclohexane, the n-octane and the butyl titanate is independently 0.5 to 70 weight percent; in a specific embodiment, the content of butyl acetate and xylene is independently 10 to 40 wt%, and the content of n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl acetate is independently 2 to 5 wt%. If the content of the organic solvent exceeds the range, the film forming property and the surface drying property of the ceramic surface material before ceramic formation can be influenced, so that the thermal cracking reaction of the ceramic surface material is influenced, the ceramic forming property of the ceramic surface material is directly influenced, and finally the self-cleaning property and the toughness of the ceramic surface material are influenced.
In the present application, the assistant is an assistant well known to those skilled in the art, and the present application is not particularly limited thereto, and in specific examples of the present application, the assistant is selected from one or more of a silane coupling agent, a wetting dispersant, and a catalytic curing agent. The content of the additives is 0.1 wt% to 3.0 wt%, and more specifically, the content of each additive in the additives is independently 0.5 wt% to 1.0 wt%. If the content of the auxiliary agent is beyond the range, the dispersibility, the coupling performance and the curing performance of the ceramic surface material can be directly influenced, so that the ceramic forming performance of the ceramic surface material can influence the binding capacity of the ceramic surface material and a matrix and the self-healing capacity of the ceramic surface material.
The filler in the present invention serves as a core component which ultimately determines the properties of the ceramic surface material. The filler in the application is composed of graphene, graphite, transition metal oxides, composite silicates, rare earth oxides, nonmetals, nonmetallic compounds, transition metal borides, whiskers and metals. The particle size of the filler is 50-900 nm.
In the filler, the graphite and the graphene are beneficial to forming a ceramic layer at normal temperature and shielding corrosive media from permeating, and the surface hardness of the base material is improved by carburizing the metal base material at high temperature; the graphite and the graphene form carbon dioxide at high temperature, and the carbon dioxide is matched with the thermal cracking temperature of the organic silicon, so that the cracked gas is favorably discharged from the ceramic layer; meanwhile, the graphene and the graphite are also helpful for promoting and catalyzing other reactions in the ceramic layer at high temperature, and generate carbide ceramic with other substances.
The transition group metal oxide can be one or more selected from zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, and the thermal expansion coefficient of the transition group metal oxide is consistent with that of the metal substrate or higher than that of the substrate; and the transition metal oxide has stronger binding capacity with the metal substrate, thereby being beneficial to the binding capacity and the thermal shock resistance of the ceramic surface material and the metal substrate.
The metal is specifically selected from one or more of aluminum, nickel, titanium, chromium, and yttrium, and in specific embodiments, the metal includes aluminum, nickel, titanium, chromium, and yttrium. The metal can adjust the thermal expansion coefficient of a ceramic layer formed by the ceramic surface material in the ceramic surface material so as to enable the ceramic layer to be closer to the metal substrate; at the same time, the above metals can form metal oxides at medium and high temperatures.
The non-metallic compound is selected from one or more of boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide. In particular embodiments, the non-metallic compound is selected from the group consisting of boron carbide, silicon boride, boron nitride, silicon nitride, a mixture of silicon carbide and boron oxide. The boron carbide, the silicon boride and the boron nitride have the characteristics of oxidation resistance, corrosion resistance, wear resistance and self lubrication at low temperature and medium and high temperature in the ceramic surface material; simultaneously, the nonmetal reacts with oxygen at medium and high temperature to generate silicon dioxide, boron oxide and the like, products react with each other to form boron glass, and pores and cracks formed by thermal cracking of organic silicon are filled in the ceramic layer by a liquid phase after the temperature of the softening point is exceeded, so that the self-repairing healing effect is realized; silicon nitride and silicon carbide are fillers that have high temperature, corrosion and wear resistance. The boron oxide, silicate in the ceramic surface material and decomposed silicon dioxide form complex phase borosilicate glass, and the complex phase borosilicate glass has different softening point temperatures along with different proportions, so that the self-repairing and self-healing temperature of the ceramic layer is adjusted to be matched with specific application environment conditions.
The non-metal is specifically selected from one or both of boron and silicon, and in specific embodiments, the non-metal is boron and silicon. The nonmetal silicon and boron have the characteristics of oxidation resistance, corrosion resistance, wear resistance and self lubrication at low temperature and medium and high temperature; meanwhile, the nonmetal reacts with oxygen at medium and high temperature to generate silicon dioxide, boron oxide and the like, products react with each other to form boron glass, and pores and cracks formed by thermal cracking of organic silicon are filled in the ceramic layer by a liquid phase after the temperature of the softening point is exceeded, so that the self-repairing healing effect is achieved.
The transition metal boride is selected from one or more of titanium boride, zirconium boride, chromium boride and nickel boride; in particular embodiments, the transition metal boride is a mixture of titanium boride, zirconium boride, chromium boride, and nickel boride. The transition metal boride has the advantages of high temperature resistance, corrosion resistance, wear resistance and higher thermal expansion coefficient, so that the transition metal boride is matched with the thermal expansion coefficient of a metal substrate; meanwhile, the glass has better compatibility with metal substrates, metal fillers and borosilicate glass.
The whisker is selected from one or two of silicon carbide whisker and silicon nitride whisker; in particular embodiments, the whiskers are selected from silicon carbide whiskers and silicon nitride whiskers. The silicon carbide whiskers and the silicon nitride whiskers are toughening substances, and can increase the toughness of a ceramic layer formed by the ceramic surface material, so that the ceramic layer is suitable for a metal substrate.
Also included among the above fillers are complex silicates selected in particular from one or more of the group consisting of copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate; the composite silicate reacts at high temperature to introduce silicon dioxide, so that the corrosion resistance, the bonding strength and the mechanical property of the ceramic surface material are improved.
The rare earth oxide in the filler may be selected in particular from cerium oxide, yttrium oxide and lanthanum oxide. The rare earth oxide can be selectively enriched in a coating formed by a ceramic surface material due to the self lattice defect, so that gaps generated in the heating process are filled, and the mutual permeation of components can be promoted.
Based on the ceramic surface material, the content of the filler is 1.0 to 50 weight percent; in a specific embodiment, the filler is present in an amount of 1.5 wt% to 40 wt%. Specifically, when the rare earth oxide is cerium oxide, yttrium oxide and lanthanum oxide, the content of cerium oxide, yttrium oxide and lanthanum oxide is independently 0.1 wt% -2 wt%; the content of the graphite is 0.1 to 3 weight percent; the content of the graphene is 0.1-3 wt%; when the metal is chromium powder, nickel powder, titanium powder, aluminum powder and yttrium powder, the content of the chromium powder, the nickel powder, the titanium powder, the aluminum powder and the yttrium powder is independently 0.1-20 wt%; when the composite silicate is copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate, the content of the copper chromium spinel, the magnesium aluminate spinel, the mullite, the nepheline, the kaolin, the kyanite, the aluminum silicate and the zirconium silicate is independently 0.1-20 wt%; when the transition metal oxide is zirconia, chromia, titania, molybdenum oxide, and niobium oxide, the zirconia, chromia, titania, molybdenum oxide, and niobium oxide are independently contained in an amount of 0.1 wt% to 20 wt%.
In a specific embodiment, when the rare earth oxide is cerium oxide, yttrium oxide and lanthanum oxide, the content of cerium oxide, yttrium oxide and lanthanum oxide is independently 0.3 wt% to 1.5 wt%; the content of the graphite is 0.2 wt% -2 wt%; the content of the graphene is 0.2 wt% -2 wt%; when the metal is chromium, nickel, titanium, aluminum and yttrium, the content of chromium, nickel, titanium, aluminum and yttrium is independently 0.2 wt% -3 wt%; when the composite silicate is copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate, the content of the copper chromium spinel, the magnesium aluminate spinel, the mullite, the nepheline, the kaolin, the kyanite, the aluminum silicate and the zirconium silicate is independently 0.2 to 3 weight percent; when the transition metal oxide is zirconia, chromia, titania, molybdenum oxide, and niobium oxide, the zirconia, chromia, titania, molybdenum oxide, and niobium oxide are independently contained in an amount of 0.1 wt% to 3 wt%. If the content of the rare earth oxide exceeds the above range, the dispersion property of the ceramic surface material and the stability of the space network structure are affected; if the content of the graphite and the graphene exceeds the range, the film-forming performance of the ceramic surface material has certain influence, and meanwhile, the corrosion resistance of the ceramic surface material is fluctuated and unstable, and the toughness of the formed ceramic surface material and the metal base material also has certain influence; if the content of the composite silicate exceeds the range, the self-healing capability, the corrosion resistance and the toughness of the ceramic surface material are influenced to a certain extent; if the content of the metal and the transition metal oxide is outside the above range, the corrosion resistance and the thermal shock resistance of the ceramic surface material may be affected to some extent.
In a specific embodiment, the non-metals are silicon and boron, in which case the silicon and boron content is independently 0.1 wt% to 20 wt%; in a specific embodiment, the silicon and boron content is independently 0.2 wt% to 3 wt%. If the content of the nonmetal component exceeds the above range, the self-healing ability of the ceramic surface material is affected, thereby affecting the corrosion resistance of the ceramic surface material.
In a specific embodiment, when the non-metallic compound is boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide, the content of the boron carbide, the silicon boride, the boron nitride, the silicon carbide and the boron oxide is independently 0.1 wt% to 20 wt%; in a specific embodiment, the content of boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide is independently 0.2 wt% to 3 wt%. If the content of the independent non-metal compound exceeds the range, the self-healing capability and the self-healing controllability of the ceramic surface material are influenced, and meanwhile, the wear resistance and the toughness of the ceramic surface material are influenced to a certain extent.
In a specific embodiment, when the whiskers are silicon carbide whiskers and silicon nitride whiskers, the content of the silicon carbide whiskers and the content of the silicon nitride whiskers are independently 0.1 wt% to 5 wt%; in a specific embodiment, the content of the silicon carbide whisker and the silicon nitride whisker is independently 0.2 wt% to 2 wt%. If the content of the independent whiskers exceeds the above range, the toughness and the thermal shock resistance of the ceramic surface material are affected to some extent.
In a specific embodiment, when the transition metal boride is titanium boride, zirconium boride, chromium boride and nickel boride, the content of the titanium boride, zirconium boride, chromium boride and nickel boride is independently 0.1 wt% to 20 wt%; in a specific embodiment, the titanium boride, zirconium boride, chromium boride and nickel boride independently comprise 0.2 wt% to 3 wt%. If the individual content of the transition metal boride is outside the above range, the thermal shock resistance, corrosion resistance and bonding ability to the substrate of the ceramic surface material may be affected to some extent.
Preferably, the ceramic surface material of the present application includes:
taking the ceramic surface material as a base, wherein the content of the organic silicon mixture is 35 wt% (wherein the content of polysilazane is 10 wt%, the content of polyborosilazane is 10 wt%, and the content of polysiloxane, polysilazane, polysilacarbozane and polyborosilazane is 3 wt%);
the content of the organic solvent is 23 wt% (wherein, the content of butyl acetate is 2 wt%, the content of xylene is 11 wt%, and the content of n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate are all 2 wt%);
the content of the auxiliary agent is preferably 1.5 wt% (wherein, the content of the silane coupling agent, the wetting dispersant and the catalytic curing agent is 0.5 wt%);
the total filler mixture content was 40.5 wt% (where boron carbide was 1.5 wt%, silicon boride was 1.5 wt%, boron nitride was 1.5 wt%, silicon carbide was 1.5 wt%, boron oxide was 1.5 wt%, titanium boride was 2 wt%, zirconium boride was 2 wt%, chromium boride was 2 wt%, nickel boride was 2 wt%, zirconium oxide was 0.6 wt%, chromium oxide was 0.8 wt%, titanium oxide was 0.8 wt%, molybdenum oxide was 0.8 wt%, niobium oxide was 0.8 wt%, copper chromium spinel was 1 wt%, magnesium aluminate spinel was 1 wt%, mullite was 1 wt%, nepheline was 1 wt%, kaolin was 1.8 wt%, kyanite was 1.8 wt%, aluminum silicate was 3 wt%, (where, 3 wt% of zirconium silicate, 0.2 wt% of graphite, 0.2 wt% of graphene, 0.4 wt% of cerium oxide, 0.4 wt% of yttrium oxide, 0.4 wt% of lanthanum oxide, 1.2 wt% of silicon carbide whiskers, 1.2 wt% of silicon nitride whiskers, 0.55 wt% of silicon powder, 0.55 wt% of boron powder, 0.2 wt% of aluminum powder, 0.2 wt% of nickel powder, 0.2 wt% of titanium powder, 0.2 wt% of chromium powder and 0.2 wt% of yttrium powder).
The term "independently" in the context of the above-mentioned components means that the content of each component can be selected within a range, and that the selection of the content between the components is not affected, but it is necessary to ensure that the total content does not exceed the total range value.
The components and the content of the components of the ceramic surface material provided by the application are optimally matched, so that the ceramic surface material as a coating material has higher comprehensive performance.
The ceramic surface material described herein may be prepared in a manner well known to those skilled in the art. In order to make the various components in the surface material more uniform, the method for preparing the ceramic surface material described herein is preferably performed according to the following steps:
mixing organic silicon with an organic solvent to obtain a composite organic silicon liquid containing the solvent; and refining the filler, mixing the refined filler with the solvent-containing composite organic silicon liquid, adding the auxiliary agent, uniformly stirring, filtering and packaging to obtain the ceramic surface material.
The application also provides the application of the ceramic surface material in an industrial furnace. The ceramic surface material can be coated on the surface of the furnace tube of the industrial furnace to form the ceramic surface material, so that the stability of the industrial furnace in the using process is protected. The industrial furnace may be a boiler, a kiln, a heating furnace, or the like, which is well known to those skilled in the art.
For further understanding of the present invention, the ceramic surface material provided by the present invention is described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Examples 1 to 10
Mixing organic silicon with an organic solvent to obtain a composite organic silicon liquid containing the solvent; and refining the filler, mixing the refined filler with the solvent-containing composite organic silicon liquid, adding the auxiliary agent, uniformly stirring, filtering and packaging to obtain the ceramic surface material. The contents of the components of the ceramic surface materials provided in examples 1 to 10 are shown in table 1.
The ceramic surface materials of the embodiments 1 to 10 are respectively sprayed on the water wall of a main combustion area of a water wall of a 1000MW power station pulverized coal boiler, the surfaces of a superheater and a reheater, the surface of a hearth water wall of a 600t/d large garbage power station boiler, the surface of a 130t/h large biomass boiler water wall and the surface of a high-temperature superheater, and the coating thickness is 30 to 100 mu m. After the product is applied for one year, the product is subjected to performance detection according to the national or industrial universal detection standard, and the detection results are shown in table 2.
Table 1 examples 1-10 table (wt%) of the contents of the components and specification data of the ceramic surface material
TABLE 2 data sheets of performance parameters for ceramic surfacing materials provided in examples 1-10
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (11)
1. A ceramic surfacing material consisting of:
the organic solvent is selected from one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane and butyl titanate;
the filler consists of graphene, graphite, transition metal oxides, composite silicates, rare earth oxides, nonmetal compounds, transition metal borides, whiskers and metals;
the rare earth oxide is cerium oxide, yttrium oxide and lanthanum oxide, and the content of cerium oxide, yttrium oxide and lanthanum oxide is 0.1-2 wt% independently;
the content of the graphite is 0.1 to 3 weight percent; the content of the graphene is 0.1-3 wt%;
the metal is chromium, nickel, titanium, aluminum and yttrium, and the content of chromium, nickel, titanium, aluminum and yttrium is independently 0.1 wt% -20 wt%;
the composite silicate is copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate, and the content of the copper chromium spinel, the magnesium aluminate spinel, the mullite, the nepheline, the kaolin, the kyanite, the aluminum silicate and the zirconium silicate is independently 0.1-20 wt%;
the nonmetal is silicon and boron, and the content of the silicon and the content of the boron are independently 0.1 to 20 weight percent;
the non-metallic compound is boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide, and the content of the boron carbide, the silicon boride, the boron nitride, the silicon carbide and the boron oxide is independently 0.1-20 wt%;
the transition metal boride is titanium boride, zirconium boride, chromium boride and nickel boride, and the content of the titanium boride, the content of the zirconium boride, the content of the chromium boride and the content of the nickel boride are 0.1 to 20 weight percent independently;
the whiskers are silicon carbide whiskers and silicon nitride whiskers, and the content of the silicon carbide whiskers and the content of the silicon nitride whiskers are 0.1-5 wt% independently;
the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, and the content of zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide is independently 0.1 wt% to 20 wt%.
2. The ceramic surface material according to claim 1, characterized in that the silicone is selected from one or more of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, polysiloxazane and polyborazane.
3. The ceramic surfacing material according to claim 1, wherein the auxiliary agent is selected from one or more of a silane coupling agent, a wetting dispersant and a catalytic curing agent.
4. The ceramic surfacing material according to any one of claims 1 to 3, wherein the filler has a particle size of 50 to 900 nm.
5. The ceramic surface material according to claim 2, characterized in that when the silicone is one or more of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, polysiloxazane and polyborazine, the content of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilocarbane and polysiloxazane is independently 0.5 to 70 wt%.
6. The ceramic surface material according to claim 2, characterized in that when the silicone is polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane, a mixture of polysilazane and polyborazane, the content of polysilazane, polysilaborazane, polysiloxane, polysiloxazane, polysilazane and polysiloxazane is independently 0.5 to 67 wt%.
7. The ceramic surface material according to claim 2 or 6, characterized in that when the silicone is polysilazane, polysiloxane, polysiloxazane, polysilazane, a mixture of polysilazane and polyborazane, the content of the silicone is 30 to 60 wt%, the content of the polysilazane is 10 to 20 wt%, and the content of the polysiloxane, polysilazane, polysilocarbazane and polyborazane is independently 2 to 5 wt%.
8. The ceramic surfacing material according to claim 1, wherein when the organic solvent is one or more of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate, the content of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate is independently 0.5 wt% to 70 wt%.
9. The ceramic surfacing material according to claim 1, wherein when the organic solvent is a mixture of butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate, the content of the butyl acetate, xylene, n-butyl ether, diethylene glycol butyl ether acetate, methylcyclohexane, n-octane, and butyl titanate is independently 0.5 wt% to 67 wt%.
10. The ceramic surface material of claim 1, wherein the rare earth oxide is cerium oxide, yttrium oxide, and lanthanum oxide, the cerium oxide, yttrium oxide, and lanthanum oxide being independently present in an amount of 0.3 wt% to 1.5 wt%;
the content of the graphite is 0.2 wt% -2 wt%; the content of the graphene is 0.2 wt% -2 wt%;
the metal is chromium, nickel, titanium, aluminum and yttrium, and the content of chromium, nickel, titanium, aluminum and yttrium is independently 0.2 wt% -3 wt%;
the nonmetal is silicon and boron, and the content of the silicon and the content of the boron are independently 0.2 to 3 weight percent;
the composite silicate is copper chromium spinel, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, aluminum silicate and zirconium silicate, and the content of the copper chromium spinel, the magnesium aluminate spinel, the mullite, the nepheline, the kaolin, the kyanite, the aluminum silicate and the zirconium silicate is independently 0.2 to 3 weight percent;
the non-metallic compound is boron carbide, silicon boride, boron nitride, silicon carbide and boron oxide, and the content of the boron carbide, the silicon boride, the boron nitride, the silicon carbide and the boron oxide is independently 0.2-3 wt%;
the transition metal boride is titanium boride, zirconium boride, chromium boride and nickel boride, and the content of the titanium boride, the content of the zirconium boride, the content of the chromium boride and the content of the nickel boride are 0.2 to 3 weight percent independently;
the whiskers are silicon carbide whiskers and silicon nitride whiskers, and the content of the silicon carbide whiskers and the content of the silicon nitride whiskers are 0.2 wt% -2 wt% independently;
the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, and the content of zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide is independently 0.2 wt% to 3 wt%.
11. A surface coating comprising a top coat and a primer, wherein the top coat is a ceramic surface material according to any one of claims 1 to 10.
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