CN111663092A - Ceramic thermal barrier coating on surface of metal substrate and application of ceramic thermal barrier coating in engine - Google Patents
Ceramic thermal barrier coating on surface of metal substrate and application of ceramic thermal barrier coating in engine Download PDFInfo
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- CN111663092A CN111663092A CN202010422866.7A CN202010422866A CN111663092A CN 111663092 A CN111663092 A CN 111663092A CN 202010422866 A CN202010422866 A CN 202010422866A CN 111663092 A CN111663092 A CN 111663092A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0234—Impregnation and coating simultaneously
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
- F01D25/005—Selecting particular materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/284—Selection of ceramic materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
- F01L3/04—Coated valve members or valve-seats
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/16—Selection of particular materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B23/00—Other engines characterised by special shape or construction of combustion chambers to improve operation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F1/00—Cylinders; Cylinder heads
- F02F1/24—Cylinder heads
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F3/00—Pistons
- F02F3/10—Pistons having surface coverings
- F02F3/12—Pistons having surface coverings on piston heads
- F02F3/14—Pistons having surface coverings on piston heads within combustion chambers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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Abstract
The invention discloses a ceramic thermal barrier coating on the surface of a metal substrate and application thereof in an engine, belonging to the technical field of ceramic coatings. The preparation method comprises the steps of sequentially preparing a bonding layer and a ceramic thermal barrier coating on the surface of the metal substrate, wherein the ceramic thermal barrier coating is prepared from Y as a raw material2O3Powder and Zr2O3The powder or the raw material for preparing the ceramic thermal barrier coating is gamma-Al2O3The chromium phosphate magnesium binder and BN powder or the raw materials for preparing the ceramic thermal barrier coating are gamma-Al2O3And SiO2.nH2And O. The ceramic layer is also coated with an oxidation catalyst, and the porosity of the oxidation catalyst is greater than that of the bonding layer; when the ceramic thermal barrier coating prepared by the invention is applied to an engine, the oxidation catalyst added in the ceramic layer can utilize excessive hydrocarbon and carbon monoxide, oxidize the hydrocarbon before the hydrocarbon is converted into carbon deposit, reduce the fuel enrichment during cold start, reduce the discharge amount of the hydrocarbon and the carbon monoxide, and prevent the occurrence of the pre-ignition phenomenon caused by the carbon deposit.
Description
Technical Field
The invention relates to the technical field of ceramic coatings, in particular to a ceramic thermal barrier coating on the surface of a metal substrate and application thereof in an engine.
Background
In order to improve the efficiency of an engine or a gas turbine and reduce carbon emission, the requirement of the combustion temperature is higher and higher, however, the too high temperature brings more severe use environment for metal parts of a heat engine, and the common single crystal or high-temperature alloy reaches the use limit and is difficult to meet the requirement. To solve this problem, thermal barrier coating technology has been widely used in recent years. The ceramic thermal barrier coating has the functions of heat insulation, wear resistance, corrosion resistance, oxidation resistance and the like, is widely applied in the fields of aerospace, aviation and energy, particularly has obvious protection effect in high-pressure turbine blades, combustion chambers and cooling flow channels of aeroengines and hot end parts of industrial gas turbines, and obviously improves the efficiency of heat engines and prolongs the cycle life. In addition, the thermal barrier coating technology can reduce heat transfer loss and improve the compression temperature in a cylinder, so that some fuels with low cetane number, high autoignition temperature and high latent heat of vaporization, such as gasoline, ethanol or methanol, can replace diesel oil to become main fuels of a compression ignition engine, realize compression ignition, improve heat efficiency and reduce soot emission.
However, during engine cold starts, the fuel enriched in the cylinder is typically needed to warm up the engine at the beginning of the emission certification cycle, but too much incompletely atomized fuel may deposit on metal surfaces and may form soot at high temperatures. Low cetane fuel compression takes advantage of the high compression ratio, large amount of exhaust gas recirculation, obtains additional heat energy, and supplies free radicals to initiate combustion. Although the compression self-ignition temperature of the fuel with low cetane number is high, the ignition temperature and the ignition energy on the surface of the fuel are low, so that the carbon deposits on a piston, an exhaust valve or a cylinder cover are easy to ignite automatically, a pre-ignition phenomenon is generated, and the emission amount of hydrocarbon and carbon monoxide is increased.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a ceramic thermal barrier coating on the surface of a metal substrate and an application thereof in an engine.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a ceramic thermal barrier coating on the surface of a metal substrate is characterized in that a bonding layer and the ceramic thermal barrier coating are sequentially prepared on the surface of the metal substrate, a catalyst containing rare earth elements, platinum, palladium and alumina is coated on the ceramic thermal barrier coating, and the coating amount of the catalyst is 1-5mg/cm2. The ceramic thermal barrier coating adopts the following three modes:
the first mode is as follows: the MCrAlY layer is used as a bonding layer, and the preparation raw material of the ceramic thermal barrier coating is Y2O3Powder and Zr2O3Y in raw material for preparing powder and ceramic thermal barrier coating2O3Content of 5-10 wt.%, Zr2O3The balance is;
the second way is: the preparation raw materials of the bonding layer are chromium phosphate magnesium binder, spherical aluminum powder, flaky aluminum powder and Cr2O3The raw material for preparing the ceramic thermal barrier coating is gamma-Al2O3Chromium phosphate magnesium binder, BN powder and preparation of ceramic thermal barrier coatinggamma-Al in the raw material2O36-14 wt.%, 67-91 wt.% of chromium magnesium phosphate binder, 1-8 wt.% of BN content;
the third mode is as follows: the preparation raw materials of the bonding layer are chromium phosphate magnesium binder, spherical aluminum powder, flaky aluminum powder and Cr2O3The raw material for preparing the ceramic thermal barrier coating is gamma-Al2O3And SiO2.nH2O, gamma-Al in raw material for preparing ceramic thermal barrier coating2O3Content 4-24 wt.%, SiO2.nH2O is the rest;
in the first mode, the chemical composition of the MCrAlY layer is as follows: 35-40 wt.% of Co, 20-24 wt.% of Cr, 8-12 wt.% of Al, 0.2-0.8 wt.% of Y, and the balance of Ni.
In the second and third modes, the content of the chromium magnesium phosphate binder in the raw materials for preparing the bonding layer is 40-75 wt.%, the content of the spherical aluminum powder is 5-15 wt.%, the content of the flake aluminum powder is 5-20 wt.%, and the content of Cr is 5-20 wt.%2O3The content is 10-35 wt.%.
The preparation raw materials of the chromium phosphate magnesium binder comprise the following components in percentage by weight: 10-15% of magnesium oxide, 18-24% of chromium sesquioxide, 11-18% of phosphoric acid and 30-52% of water, and the raw material components are fully mixed and dissolved to obtain the chromium phosphate magnesium binder.
The bonding layer and the ceramic thermal barrier coating are prepared by adopting a cold spraying process or an atmospheric plasma spraying process; the thickness of the bonding layer is 10-200 μm, and the thickness of the ceramic thermal barrier coating is 20-100 μm; the porosity of the bonding layer is 2-5%, the porosity of the ceramic thermal barrier coating is 10-35%, and the thermal conductivity of the ceramic thermal barrier coating is 0.3-0.9W/mK.
The catalyst is coated on the surface of the ceramic thermal barrier coating by adopting a dipping method, and the dipping method comprises the following steps:
(1) preparing materials: preparing a nitric acid solution containing platinum and palladium, wherein the molar ratio of the platinum to the palladium is (0.8-2); adding alumina powder (gamma-Al) accounting for 35-75% of the weight of the solution into a nitric acid solution containing platinum and palladium2O3) Stirring and mixing for 10-12 hours to obtain a noble metal solution containing alumina;adding cerium nitrate, a copper molecular sieve and epoxy resin which respectively account for 1-5%, 2-5% and 3-5% of the weight of the alumina-containing noble metal solution, and uniformly mixing to obtain a mixed material;
(2) preparing precursor slurry of the catalyst: mixing the mixed material obtained in the step (1), an adhesive and water in proportion, and stirring for 5-10 hours in a ball milling or sanding mode to form a colloid, thus obtaining precursor slurry of the catalyst;
(3) coating: coating the precursor slurry of the catalyst obtained in the step (2) on the surface of the ceramic thermal barrier coating in a negative pressure adsorption or nitrogen purging mode;
(4) drying and roasting: and (3) placing the ceramic thermal barrier coating coated with the catalyst precursor slurry in the step (3) in a kiln at the temperature of 520 ℃ and 580 ℃ for firing for 3-5 hours.
In the step (2), the weight ratio of the total weight of the mixed material and the adhesive to the water is (18-22): 1, the weight ratio of the mixed material to the adhesive is (4-6): 2, the adhesive is sodium silicate or calcium silicate or chromium magnesium phosphate;
in the step (3), the ratio of the weight of the noble metals (platinum and palladium) in the precursor slurry of the catalyst to the volume of the ceramic thermal barrier coating to be coated is (15g-35 g): 1L; and (4) after the calcination, the bonding strength between the catalyst and the thermal barrier ceramic coating is not less than 25 MPa.
The ceramic thermal barrier coating is arranged on a metal surface which is in contact with combustion gas in an engine, and particularly can be arranged on the surface of a combustion chamber at the top of a piston, an inlet valve, an exhaust valve, the surface of a combustion chamber of a cylinder cover, an exhaust passage, an exhaust manifold, a turbine shell, the surface of a waste gas bypass valve, variable-geometry turbine nozzle blades, a nozzle ring retainer and turbine blades of the engine.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the composition of the bonding layer and the ceramic thermal barrier coating is optimized, so that the ceramic thermal barrier coating has enough tensile shear strength, the bonding strength of the prepared ceramic thermal barrier coating and the base material is higher than 30MPa, and the engine has enough reliability and durability during the operation.
2. The present invention coats a quantity of catalyst on the ceramic thermal barrier coating, the catalyst is capable of oxidizing excessive hydrocarbons and carbon monoxide in the combustion chamber and the exhaust gas flow passage during the cold start of the engine, the energy generated by the oxidation exothermic reaction will further accelerate the post-treatment preheating; the catalyst coated ceramic thermal barrier coating also prevents pre-ignition due to carbon deposition when the engine is operated at high load.
3. The invention controls the porosity of the ceramic thermal barrier coating to be 10-35% by optimizing the composition of the ceramic thermal barrier coating, and controls the coating amount of the catalyst on the ceramic thermal barrier coating to be 1-5mg/cm2Under the matching of the porosity of the ceramic thermal barrier coating and the coating amount of the catalyst, on one hand, the sufficient heat insulation effect (0.3-0.9W/mK) of the ceramic thermal barrier coating is ensured, and on the other hand, the catalytic chemical effect of the catalyst on the coating is not influenced.
4. The invention adopts the dipping method to prepare the catalyst on the ceramic thermal barrier coating, and ensures the binding force between the catalyst and the coating. The bonding strength between the catalyst and the ceramic coating carrier is not less than 25 MPa.
5. The catalyst coated on the ceramic thermal barrier coating can oxidize hydrocarbon and carbon monoxide in an exhaust gas flow passage during the cold start and the idling of a supercharged engine, and has the greatest advantage that the hydrocarbon and the carbon monoxide in the engine exhaust gas can be subjected to oxidation reaction to generate CO at low temperature2And H2O, which is effective in reducing the concentration of hydrocarbons and carbon monoxide in the exhaust gas flow passage.
Drawings
FIG. 1 is a ceramic thermal barrier coating prepared in example 1.
Detailed Description
For a further understanding of the present invention, the following description is given in conjunction with the examples which are set forth to illustrate, but are not to be construed to limit the present invention, features and advantages.
The invention will now be described in further detail with reference to examples.
The invention relates to a ceramic thermal barrier coating coated with a catalyst and applied to an engine, which comprises a bonding layer matched with the thermal expansion coefficient of a metal substrate, a ceramic layer and an oxidation catalyst coated on the surface of the ceramic layer.
The oxidation catalyst on the ceramic layer is an active material that can selectively oxidize hydrocarbons and carbon monoxide in the combustion chamber and exhaust flow channels, and due to the proximity of the combustion gases and the high turbulence, the catalyst on the surfaces of the combustion chamber, exhaust flow channels, and turbine blades will be heated earlier during cold start than the adjacent catalyst and the vehicle bottom catalyst.
The overall thermal conductivity of the ceramic thermal barrier coating prepared by the method is 0.3-0.9W/mK, and the total thickness of the thermal barrier coating except the ceramic thermal barrier coating on the turbine blade is 0.1-0.9 mm.
In the following examples, the raw materials for preparing the chromium phosphate magnesium binder consist of (wt.%): 10-15% of magnesium oxide, 18-24% of chromium sesquioxide, 11-18% of phosphoric acid and 30-52% of water, and the raw material components are fully mixed and dissolved to obtain the chromium phosphate magnesium binder.
In the following examples, the catalyst was applied by dipping, as follows:
(1) preparing materials: preparing a nitric acid solution containing platinum and palladium, wherein the molar ratio of the platinum to the palladium is 1: 1; adding alumina powder (gamma-Al) accounting for 50 percent of the weight of the solution into nitric acid solution containing platinum and palladium2O3) Mixing for 10 hours to obtain a noble metal solution containing alumina; adding cerium nitrate, a copper molecular sieve and epoxy resin which respectively account for 2%, 3% and 3.5% of the weight of the alumina-containing noble metal solution, and uniformly mixing to obtain a mixed material;
(2) mixing the mixed material obtained in the step (1), an adhesive (sodium silicate or calcium silicate or chromium magnesium phosphate) and water in proportion, and stirring for 6 hours in a ball milling or sanding mode to form colloid to obtain precursor slurry of the catalyst; the weight ratio of the total weight of the mixed material and the adhesive to the water is 20: 1, the weight ratio of the mixed material to the adhesive is 5: 2;
(3) coating: coating the precursor slurry of the catalyst obtained in the step (2) on the surface of the ceramic thermal barrier coating in a negative pressure adsorption or nitrogen purging mode; the proportion of the weight of noble metals (platinum and palladium) in the precursor slurry to the volume of the ceramic thermal barrier coating to be coated in coating is 25 g: 1L;
(4) drying and roasting: and (4) placing the ceramic thermal barrier coating coated with the catalyst precursor slurry in the step (3) in a kiln at 550 ℃ for firing for 3-5 hours, wherein the bonding strength between the catalyst and the thermal barrier ceramic coating after firing is not less than 25 MPa.
Example 1:
as shown in figure 1, an MCrAlY bonding layer and a TBC top layer are sprayed on a turbine housing by adopting atmospheric plasma spraying, and the MCrAlY bonding layer comprises the specific components of 37.0 wt% of Co, 21.8 wt% of Cr, 9.36 wt% of Al, 0.52 wt% of Y and the balance of Ni. The TBC top layer has a specific composition of Y2O3Zr content 7 wt%2O3And (4) the balance. The coating thickness is uniform, the MCrAlY bonding layer thickness is 0.184mm, the TBC top layer thickness is 0.095mm, the bonding layer tissue structure is compact, the bonding layer porosity is 3.5%, the top layer porosity is 12.6%, and the distribution is uniform.
This example tested a bond strength of 36MPa between the TBC top layer and the substrate at room temperature due to the chemical bonding that occurs between the coating and the substrate, thereby increasing the bonding force.
The MCrAlY bonding layer is arranged between the base metal and the thermal barrier ceramic surface layer, and has the double effects of improving the physical compatibility of the coating and the base and resisting oxidation, and the thermal conductivity of the ceramic thermal barrier layer is 0.35W/mK.
Coating a catalyst on the surface of the TBC of the top layer, and drying the TBC, wherein the coating amount of the catalyst is 2mg/cm2Forming a TBC ceramic thermal barrier coating with a catalyst. The adhesive strength between the catalyst and the ceramic coating is not less than 25 MPa.
Example 2:
a bonding layer and a top layer are sprayed on the turbine shell in a cold spraying mode, and the bonding layer comprises 43-71 wt% of chromium phosphate magnesium binder, 5-15 wt% of spherical aluminum powder, 7-13 wt% of flake aluminum powder and Cr2O3The content is 16 wt% -30 wt%. The top layer is embodied asIs divided into gamma-Al2O36 to 14 weight percent of the binder, 67 to 91 weight percent of the chrome magnesium phosphate binder and 1 to 8 weight percent of BN. The thickness of the coating is uniform, the thickness of the bonding layer is 20-60um, and the thickness of the top layer is 10-50 μm.
This example tests that the bond strength between the top layer and the substrate was 35.5MPa at room temperature.
The bond coat is between the turbine casing and the top layer and has the effect of improving the physical compatibility of the coating with the substrate, oxidation resistance, and corrosion resistance.
The top layer contains gamma-Al2O3Has higher specific surface area and can support more catalysts. BN has certain temperature resistance and corrosion resistance, and the thermal conductivity of the ceramic thermal barrier layer is about 0.3W/mK.
The weight of the catalyst coated on the surface of the coating can reach 1.0-2.3g, and the bonding strength between the catalyst and the ceramic coating is not less than 25 MPa.
Example 3:
a bonding layer and a top layer are sprayed on the turbine shell in a cold spraying mode, and the bonding layer comprises the specific components of 40-65 wt% of chromium phosphate magnesium binder, 7-12 wt% of spherical aluminum powder, 5-16 wt% of flake aluminum powder and Cr2O3The content is 10 wt% -33 wt%. The top layer comprises gamma-Al2O34 to 24 weight percent of SiO2.nH2The O content is 60 to 90 weight percent. The thickness of the coating is uniform, the thickness of the bonding layer is 10-70um, and the thickness of the top layer is 20-65 μm.
This example tests a bond strength between the TBC top layer and the substrate of 35MPa at room temperature.
The bond coat is between the turbine casing and the top layer and has the effect of improving the physical compatibility, oxidation and corrosion resistance of the coating and the substrate, and the thermal conductivity of the ceramic thermal barrier layer is about 0.35W/mK.
The top layer contains gamma-Al2O3Has higher specific surface area and can support more catalysts. SiO 22.nH2O has the characteristics of strong binding power and high temperature resistance, and has a relatively large specific surface area due to the fine (10-20nm) colloidal particlesThe area increases the attachment area of the catalyst on a certain basis.
The weight of the catalyst coated on the surface of the coating can reach 2.6g-4.4g, and the bonding strength between the catalyst and the ceramic coating is not less than 25 MPa.
The thermal shock performance test of 800 ℃ water quenching was performed after the ceramic thermal barrier coating was prepared on the substrate (without the catalyst) in examples 1-3, and the results show that the bonding layer and the top layer did not fall off after the 10 th thermal shock, the 50 th thermal shock, and the 100 th thermal shock.
After the ceramic thermal barrier coating is coated with the catalyst, the catalyst can oxidize hydrocarbon and carbon monoxide in an exhaust gas flow passage during the cold start and the idling of a supercharged engine to generate CO by reaction2And H2O, which is effective in reducing the concentration of hydrocarbons and carbon monoxide in the exhaust gas flow passage.
Tests on the ceramic coatings coated with the catalysts prepared in the above examples 1 to 3 show that the sample coated with the catalyst of the present invention can function at a low temperature of 50 ℃, and when the temperature reaches 100 ℃, the temperature of the exhaust gas can be increased by 50 ℃ to 120 ℃, and simultaneously, the concentrations of hydrocarbons and carbon monoxide in the exhaust gas can be reduced by more than 20% under the working conditions of cold start and idling operation of a supercharged engine at a low temperature.
Claims (10)
1. A ceramic thermal barrier coating on the surface of a metal substrate is characterized in that: the surface of the metal substrate is sequentially prepared with a bonding layer and a ceramic thermal barrier coating, the ceramic thermal barrier coating is coated with a catalyst, and the ceramic thermal barrier coating adopts the following three modes:
the first mode is as follows: the MCrAlY layer is used as a bonding layer, and the preparation raw material of the ceramic thermal barrier coating is Y2O3Powder and Zr2O3Y in raw material for preparing powder and ceramic thermal barrier coating2O3Content of 5-10 wt.%, Zr2O3The balance is;
the second way is: the preparation raw materials of the bonding layer are chromium phosphate magnesium binder, spherical aluminum powder, flaky aluminum powder and Cr2O3The raw material for preparing the ceramic thermal barrier coating is gamma-Al2O3The chrome magnesium phosphate binder, the BN powder and the gamma-Al in the raw materials for preparing the ceramic thermal barrier coating2O36-14 wt.%, 67-91 wt.% of chromium magnesium phosphate binder, 1-8 wt.% of BN content;
the third mode is as follows: the preparation raw materials of the bonding layer are chromium phosphate magnesium binder, spherical aluminum powder, flaky aluminum powder and Cr2O3The raw material for preparing the ceramic thermal barrier coating is gamma-Al2O3And SiO2.nH2O, gamma-Al in raw material for preparing ceramic thermal barrier coating2O3Content 4-24 wt.%, SiO2.nH2O is the rest;
the catalyst is a catalyst containing rare earth elements, platinum, palladium and alumina, and the coating amount of the catalyst is 1-5mg/cm2。
2. The metallic substrate surface ceramic thermal barrier coating of claim 1, wherein: in the first mode, the chemical composition of the MCrAlY layer is as follows: 35-40 wt.% of Co, 20-24 wt.% of Cr, 8-12 wt.% of Al, 0.2-0.8 wt.% of Y, and the balance of Ni.
3. The metallic substrate surface ceramic thermal barrier coating of claim 1, wherein: in the second and third modes, the content of the chromium magnesium phosphate binder in the raw materials for preparing the bonding layer is 40-75 wt.%, the content of the spherical aluminum powder is 5-15 wt.%, the content of the flake aluminum powder is 5-20 wt.%, and the content of Cr is 5-20 wt.%2O3The content is 10-35 wt.%.
4. The metallic substrate surface ceramic thermal barrier coating of claim 1, wherein: the preparation raw materials of the chromium phosphate magnesium binder comprise the following components in percentage by weight: 10-15% of magnesium oxide, 18-24% of chromium sesquioxide, 11-18% of phosphoric acid and 30-52% of water, and the raw material components are fully mixed and dissolved to obtain the chromium phosphate magnesium binder.
5. The metallic substrate surface ceramic thermal barrier coating of any of claims 1-4, wherein: the bonding layer and the ceramic thermal barrier coating are prepared by adopting a cold spraying process or an atmospheric plasma spraying process; the thickness of the bonding layer is 10-200 μm, and the thickness of the ceramic thermal barrier coating is 20-100 μm; the porosity of the bonding layer is 2-5%, the porosity of the ceramic thermal barrier coating is 10-35%, and the thermal conductivity of the ceramic thermal barrier coating is 0.3-0.9W/mK.
6. The metallic substrate surface ceramic thermal barrier coating of claim 1, wherein: the catalyst is coated by adopting an impregnation method, and the impregnation method comprises the following steps:
(1) preparing materials: preparing a nitric acid solution containing platinum and palladium, wherein the molar ratio of the platinum to the palladium is (0.8-2): 1; adding alumina powder (gamma-Al) accounting for 35-75% of the weight of the solution into a nitric acid solution containing platinum and palladium2O3) Stirring and mixing for 10-12 hours to obtain a noble metal solution containing alumina; adding cerium nitrate, a copper molecular sieve and epoxy resin which respectively account for 1-5%, 2-5% and 3-5% of the weight of the alumina-containing noble metal solution, and uniformly mixing to obtain a mixed material;
(2) preparing precursor slurry of the catalyst: mixing the mixed material obtained in the step (1), an adhesive and water in proportion, and stirring for 5-10 hours in a ball milling or sanding mode to form a colloid, thus obtaining precursor slurry of the catalyst;
(3) coating: coating the precursor slurry of the catalyst obtained in the step (2) on the surface of the ceramic thermal barrier coating in a negative pressure adsorption or nitrogen purging mode;
(4) drying and roasting: and (3) placing the ceramic thermal barrier coating coated with the catalyst precursor slurry in the step (3) in a kiln at the temperature of 520 ℃ and 580 ℃ for firing for 3-5 hours.
7. The metallic substrate surface ceramic thermal barrier coating of claim 6, wherein: in the step (2), the weight ratio of the total weight of the mixed material and the adhesive to the water is (18-22): 1, the weight ratio of the mixed material to the adhesive is (4-6): 2, the adhesive is sodium silicate or calcium silicate or chromium magnesium phosphate.
8. The metallic substrate surface ceramic thermal barrier coating of claim 6, wherein: in the step (3), the ratio of the weight of the noble metals (platinum and palladium) in the precursor slurry of the catalyst to the volume of the ceramic thermal barrier coating to be coated is (15g-35 g): 1L; and (4) after the calcination, the bonding strength between the catalyst and the thermal barrier ceramic coating is not less than 25 MPa.
9. Use of a metal substrate surfaced ceramic thermal barrier coating in an engine according to claim 1, characterized in that: the ceramic thermal barrier coating is disposed on a metal surface in contact with combustion gases in an engine.
10. Use of a metal substrate surfaced ceramic thermal barrier coating in an engine according to claim 9, characterized in that: the ceramic thermal barrier coating is arranged on the surface of a combustion chamber on the top of a piston of the engine, an inlet valve, an exhaust valve, the surface of a combustion chamber of a cylinder cover, an exhaust passage, an exhaust manifold, a turbine shell, the surface of a waste gas bypass valve, a variable-geometry turbine nozzle blade, a nozzle ring retainer and a turbine blade.
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