CN115584463A - Molten salt corrosion resistant thermal barrier coating and preparation method thereof - Google Patents
Molten salt corrosion resistant thermal barrier coating and preparation method thereof Download PDFInfo
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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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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
- C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- 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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- 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
- C23C4/129—Flame spraying
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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
Abstract
The invention relates to a molten salt corrosion resistant thermal barrier coating and a preparation method thereof, and the thermal barrier coating resists CMAS and CMAS + NaVO 3 The molten salt corrosion layer is a composite ceramic layer formed by spraying composite oxide/YSZ mixed powder, and the composite oxide powder contains Al 2 O 3 And SiO 2 、TiO 2 MgO and CaO nucleating agent, and the prepared compoundThe ceramic-containing layer contains 5wt.% to 15wt.% of composite oxide; second phase Al when the coating is in service 2 O 3 The method reacts with liquid molten salt quickly to generate an anorthite blocking layer with a high melting point, the reaction process is accelerated by the introduced nucleating agent, the molten salt can be prevented from permeating and eroding the interior of the thermal barrier coating by less addition of the composite oxide, and the CMAS and CMAS + NaVO resistance of the thermal barrier coating is improved remarkably 3 Corrosion performance.
Description
Technical Field
The invention belongs to the field of thermal barrier coating protection, and relates to a molten salt corrosion resistant thermal barrier coating and a preparation method thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Currently, the most widely used thermal barrier coatings are based on 8YSZ ceramic materials, which benefit from their superior combination of properties, including lower thermal conductivity, higher coefficient of thermal expansion, higher fracture toughness and better phase stability. When the thermal barrier coating is in service at high temperature, the working environment is harsh, and the spalling failure mechanism of the coating is complex, including high-temperature phase change of the ceramic layer, high-temperature sintering of the ceramic layer, instability and thickening of the TGO layer and the like. In addition, when the turbine engine is used in the environment with much sand dust, volcanic ash and haze for a long time, the surface of the thermal barrier coating can be continuously accumulated with glassy sediments, and the main components of the glassy sediments are CaO, mgO and Al 2 O 3 And SiO 2 Abbreviated as Calcium Magnesium Aluminosilicate (CMAS). The CMAS is melted in a high-temperature working environment of 1200 ℃ or above, and continuously infiltrates and erodes the inside of the ceramic layer along defect channels such as pores, microcracks, interlayer weak bonding interfaces and the like on the surface of the ceramic layer. CMAS molten salt and YSZ material produce thermo-chemical reaction (Y) 2 O 3 High temperature desolventizing) and thermo-mechanical action (CMAS solidification filling coating porosity, microcracks), premature induction of YSZ ceramic layer t' -ZrO 2 →m-ZrO 2 Phase change, reduced strain tolerance of YSZ ceramic layer, and accelerated coating peelingFailure severely limits the service life of the thermal barrier coating.
In addition, when the engine uses fuel containing impurities such as vanadium, sulfur, sodium, etc. (combustion exhaust gas containing SO) 2 、V 2 VO 5 ) Or Na generated by working in ocean salt fog corrosive environment 2 SO 4 、NaVO 3 And the corrosive molten salt can be adsorbed on the surface of the thermal barrier coating. After the molten salts are compounded with CMAS sediments, the melting point and viscosity of CMAS are further reduced, the penetration corrosion speed and depth of the compounded molten salts are aggravated, the high-temperature stability of the thermal barrier coating is damaged, and the service performance of an engine is seriously weakened.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a composite material with CMAS resistance and CMAS + NaVO resistance 3 The thermal barrier coating corroded by molten salt is prepared by adding a small amount of second-phase Al into a ceramic layer 2 O 3 And a nucleating agent which rapidly reacts with high-temperature molten salt to generate an anorthite blocking layer with a high melting point, so that CMAS and CMAS + NaVO are effectively slowed down 3 The penetration speed of molten salt is reduced, and the CMAS + NaVO are reduced 3 The penetration depth of the molten salt is improved, and the thermal barrier coating on CMAS and CMAS + NaVO is improved 3 High temperature thermal stability in a molten salt environment. Al reduction by addition of nucleating agents 2 O 3 The amount of the thermal barrier coating is reduced, and the comprehensive performance of the thermal barrier coating is improved.
In order to achieve the above object, the technical solution of the present invention is as follows:
in a first aspect of the invention, there is provided a molten salt corrosion resistant thermal barrier coating comprising a bond coat and a molten salt corrosion resistant layer; wherein the molten salt corrosion resistant layer is a composite ceramic layer with a laminated structure and is formed by YSZ (6-8 wt.% Y) 2 O 3 Stabilized ZrO 2 ) Powder and composite oxide powder are mixed and deposited, and the composite oxide powder is formed by Al 2 O 3 And a nucleating agent.
Furthermore, in the molten salt corrosion resistant layer, the mass fraction of the composite oxide is 5% -15%, and the balance is YSZ.
Further, in the composite oxide powder, al 2 O 3 In mass percent ofThe ratio is 90wt.% to 97wt.%, and the rest is nucleating agent. Al (Al) 2 O 3 The primary particle size of (a) may be 30 to 60 μm; the primary particle size of the nucleating agent may be 5 to 15 μm.
Further, the nucleating agent is SiO 2 、TiO 2 One or more of MgO and CaO.
Further, the particle size of the composite oxide powder is 20-80 μm. Furthermore, the porosity of the molten salt corrosion resistant layer is not particularly limited and can be between 5% and 20%.
Furthermore, the bonding layer material can be an MCrAlY material system, and the thickness of the bonding layer is 100-150 mu m.
In one implementation, the thermal barrier coating further comprises a first thermal barrier layer; the bonding layer, the first heat insulation layer and the molten salt corrosion resistant layer are sequentially stacked to form the thermal barrier coating.
Further, the first heat insulation layer is of a layered structure and is made of other heat insulation ceramic materials such as YSZ and rare earth zirconate.
Furthermore, the thickness of the first heat insulation layer is 100-200 mu m, and the molten salt corrosion resistant layer is used for resisting CMAS and CMAS + NaVO 3 A molten salt corrosion layer, preferably deposited to a thickness of 30 to 90 μm; and, the first thermal insulation layer and the anti-CMAS and CMAS + NaVO 3 The thickness ratio of the molten salt corrosion layer is 1.5-3, so that the composite oxide/YSZ composite ceramic layer can resist CMAS and CMAS + NaVO 3 The thermal barrier coating is guaranteed to have excellent heat insulation performance and fracture toughness on the basis of molten salt corrosion.
In one implementation, the anti-CMAS and CMAS + NaVO provided by the invention 3 In the thermal barrier coating corroded by the molten salt, the composite oxide/YSZ mixed powder is directly used above the bonding layer to form a ceramic thermal insulation surface layer with a single-layer structure, the thickness is 100-300 mu m, the thermal conductivity is lower than 2.0W/(m x K), and the thermal barrier coating has a better thermal insulation effect.
In a second aspect of the present invention, a method for preparing a molten salt corrosion resistant thermal barrier coating is provided, which comprises the following steps: and preparing the bonding layer and the molten salt corrosion resistant layer by spraying.
Further, the method also comprises the step of preparing the first heat insulation layer by means of spraying.
Further, the adhesive layer is prepared by any one of low-pressure plasma spraying, vacuum plasma spraying, supersonic flame spraying and cold spraying.
Further, the first heat insulation layer is prepared by spraying through any one method of atmospheric plasma spraying, vacuum plasma spraying, supersonic plasma spraying and plasma physical vapor deposition.
Further, the molten salt corrosion resistant layer is prepared by spraying through any one of the methods of atmospheric plasma spraying, vacuum plasma spraying, supersonic plasma spraying and plasma physical vapor deposition
In one embodiment, the bond coat and the molten salt corrosion resistant layer are sprayed in sequence. And directly spraying the molten salt corrosion resistant layer on the bonding layer to form a heat insulation surface layer with a laminated structure and a single ceramic structure.
In one embodiment, the bonding layer, the first heat insulation layer with the laminated structure and the molten salt corrosion resistant layer with the laminated structure are prepared by spraying in sequence to form the ceramic heat insulation surface layer with the double ceramic structure.
The thermal barrier coating provided by the invention has the advantages that the optimized addition amount of the composite oxide can ensure enough amount of Al 2 O 3 With CMAS and CMAS + NaVO 3 The molten salt is uniformly contacted and rapidly reacts with the liquid molten salt to generate an anorthite blocking layer with a high melting point, and the introduced nucleating agent accelerates the reaction process, so that the small Al content 2 O 3 The addition amount can prevent the molten salt from invading into the heat barrier coating, and the penetration speed and the penetration depth of the molten salt are greatly reduced. Smaller Al 2 O 3 The addition amount still enables the thermal insulating surface layer to have lower thermal conductivity, larger thermal expansion coefficient and higher strain tolerance. The first thermal insulation layer YSZ has excellent comprehensive performance, good thermal insulation performance, good fracture toughness, good thermal shock resistance, good phase stability and a thermal expansion coefficient which is closer to that of the bonding layer, and meets the working requirement of long service life; although the first thermal insulation layer and the composite oxide/YSZ composite ceramic layer material system are different, the smaller Al 2 O 3 The addition amount enables the two layers of components to realize gradient transition, the thermal mismatching stress between the two layers can be relieved, and the interlayer bonding strength of the double ceramic layers is ensured. The invention provides the anti-CMAS and CMAS + NaVO 3 The thermal barrier coating corroded by the molten salt has the characteristics of low thermal conductivity, high fracture toughness and good high-temperature thermal stability on the whole, and can exert the CMAS and CMAS + NaVO resistance of the composite oxide/YSZ composite ceramic layer 3 On the basis of molten salt corrosion, the heat insulation performance and the strain tolerance of the thermal barrier coating are guaranteed, and the service life of the thermal barrier coating is prolonged. The invention provides the anti-CMAS and CMAS + NaVO 3 The thermal barrier coating corroded by the molten salt takes low-cost industrialized YSZ powder as a raw material, the composite oxide powder is simple to prepare, and Al 2 O 3 The addition amount is small, the coating preparation process is short, and the industrial application is expected to be rapidly realized.
The beneficial effects of the invention are as follows:
(1) The invention adds Al into YSZ powder 2 O 3 And nucleating agent, al 2 O 3 With CMAS or CMAS + NaVO 3 The fused salt reacts quickly to generate an anorthite blocking layer with high melting point, and can effectively resist CMAS and CMAS + NaVO 3 Effect of molten salt corrosion. Addition of nucleating agent accelerates the reaction process, resulting in small additions of Al 2 O 3 The molten salt can be prevented from invading into the heat barrier coating, and the penetration speed and the penetration depth of the molten salt are greatly reduced.
(2)Al 2 O 3 The nucleating agent is used in a specific amount range so that Al is contained 2 O 3 Can generate enough closely knit anorthite blocking layer in order to prevent the fused salt to the inside invasion of heat barrier coating, simultaneously, the composition of this quantity scope again ensures first insulating layer and anti fused salt corrosion coating realizes the gradient transition, alleviates the thermal mismatch stress between two-layer, guarantees the interlayer bonding strength of two ceramic layers. The dosage of the nucleating agent ensures Al 2 O 3 And generating an anorthite plugging layer with enough thickness.
(3) The thickness of the first heat-insulating layer and the molten salt corrosion resistant layer and the layer thickness ratio of the first heat-insulating layer and the molten salt corrosion resistant layer ensure that the CMAS and CMAS + NaVO resistance of the composite oxide/YSZ composite ceramic layer is exerted 3 Molten salt corrosionOn the basis of corrosion, the thermal barrier coating is guaranteed to have excellent heat insulation performance and fracture toughness.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows that the invention provides an anti-CMAS and CMAS + NaVO 3 Schematic structural diagram of a molten salt corroded thermal barrier coating; wherein, 1, a substrate; 2. a bonding layer; 3. a first insulating layer; 4. an anti-molten salt corrosion layer;
FIG. 2 is a photograph showing the cross-sectional morphology and Ca penetration of the thermal barrier coating CMAS with single ceramic structure in example 1 after 5 hours of high temperature corrosion, wherein the gray black layer in the coating is Al 2 O 3 A base composite oxide;
FIG. 3 is an XRD picture of a single ceramic structure thermal barrier coating CMAS after 5 hours of high temperature corrosion in embodiment 1;
FIG. 4 is a single ceramic structure thermal barrier coating CMAS + NaVO in embodiment 1 3 After corrosion at high temperature for 5 hours, the cross section appearance and Ca element permeation picture of the coating are shown, and the rod-shaped object on the surface of the coating is anorthite;
FIG. 5 is a photograph of 13wt.% composite oxide/YSZ-YSZ dual ceramic structure thermal barrier coating in example 2.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Comparative example 1
And (3) carrying out deoiling and sand blasting roughening pretreatment on the high-temperature alloy matrix. Preparing NiCoCrAlY bonding layer with thickness of 100-150 μm on the surface of high-temperature alloy substrate by atmospheric plasma spraying, wherein the spraying current is 700-850A, the voltage is 30-40V, and the flow of main gas and argon is 40-60 L.min -1 Auxiliary gas helium flow of 6-9 L.min -1 3-6 L.min of carrier gas argon flow -1 Delivery ofThe powder rate is 15-30 g.min -1 The spraying distance is 100-140 mm. Preparing a YSZ ceramic layer with the thickness of 300 mu m on the surface of the bonding layer by adopting atmospheric plasma spraying, wherein the spraying current is 700-850A, the voltage is 30-40V, and the flow of main gas argon is 40-60 L.min -1 Auxiliary gas helium flow of 6-9 L.min -1 3-6 L.min of carrier gas argon flow -1 The powder feeding rate is 15-30 g.min -1 The spraying distance is 100-140 mm.
Preparation of a molar ratio of 45SiO 2 -33CaO-13AlO 1.5 -9MgO in CMAS powder and mixed with alcohol to form CMAS suspension. The suspension was uniformly applied to the surface of the ceramic layer, dried for 30 minutes, and carefully weighed so that the CMAS coating density was 35mg/cm 2 . The coating was then subjected to 1250 c high temperature corrosion for 5 hours. The result shows that the YSZ ceramic coating is completely penetrated and destroyed by CMAS molten salt, namely the penetration depth reaches-300 mu m.
Weighing the CMAS powder prepared above and NaVO 3 The powders were mixed uniformly in a mass ratio of 9:1. In order to ensure that the powder is uniformly mixed, the powder can be mixed by a ball mill for 12-48 h. Mixing the mixed powder with alcohol to form CMAS + NaVO 3 And (3) suspension. The suspension is evenly coated on the surface of the ceramic layer and then dried for 30 minutes, and the ceramic layer is carefully weighed to ensure that CMAS + NaVO 3 The coating density was 35mg/cm 2 . The coating was then subjected to 1250 c high temperature corrosion for 5 hours. The results show that the YSZ ceramic coating is completely coated by CMAS + NaVO 3 The molten salt is broken by penetration, namely the penetration depth reaches 300 mu m.
Example 1
Separately weighing Al 2 O 3 Powder and SiO 2 Powder of Al 2 O 3 Powder particle size of about 40 μm, siO 2 The powder has a particle size of about 10 μm, and is spray dried to obtain composite oxide powder (sieving particle size of 30-60 μm), al 2 O 3 The mass fraction accounts for 97 percent, and the process can be realized by using any currently known powder mixing and granulating technology; respectively weighing YSZ powder and composite oxide powder, and mixing to obtain composite ceramic powder with composite oxide powder mass fraction of 13%. And in order to ensure that the powder is uniformly mixed, performing 24-hour ball mill mixing.
And preparing a bonding layer and a 13wt.% composite oxide/YSZ composite ceramic coating with the thickness of-300 mu m by spraying according to the process parameters of the comparative case to form the thermal barrier coating with a single ceramic structure. CMAS and CMAS + NaVO were performed according to the comparative cases 3 And (4) molten salt corrosion test. The results show that the CMAS corrosion penetration distance of the 13wt.% composite oxide/YSZ composite ceramic layer is about 20 μm, CMAS + NaVO 3 The corrosion penetration distance is about 22 mu m, and excellent CMAS and CMAS + NaVO resistance is shown 3 Molten salt corrosion performance.
Example 2
A 13wt.% composite oxide/YSZ mixed powder and a bonding layer were prepared according to example 1. On the surface of the bonding layer, a first thermal insulation YSZ layer with the thickness of 170 mu m and a 13wt.% composite oxide/YSZ ceramic layer with the thickness of 90 mu m are sequentially sprayed and prepared by using the process parameters of a comparative example to form a thermal barrier coating (as shown in figure 5) with a double-ceramic structure, so that the addition of Al is further reduced 2 O 3 The thermal conductivity and the thermal mismatching of the thermal barrier coating are influenced, and the CMAS and CMAS + NaVO resistance of the composite oxide/YSZ composite ceramic layer is exerted 3 And the excellent heat insulation performance and fracture toughness of the thermal barrier coating are guaranteed on the basis of molten salt corrosion. CMAS and CMAS + NaVO were performed according to the comparative cases 3 And (4) molten salt corrosion test. The results show that the CMAS corrosion penetration distance of the thermal barrier coating with the 13wt.% composite oxide/YSZ-YSZ dual-ceramic structure is about 21 mu m, and the CMAS + NaVO 3 The etch penetration distance was about 23 μm.
As can be seen from FIGS. 2-4, the YSZ ceramic coating is completely coated by CMAS and CMAS + NaVO 3 The molten salt is penetrated and broken, and Ca element in the CMAS is diffused to the bottom surface of the ceramic layer from the surface of the ceramic layer. The addition of 13wt.% of composite oxide promotes the generation of an anorthite blocking layer at a molten salt-coating interface, and effectively blocks CMAS and CMAS + NaVO 3 Molten salt infiltration, ca diffusion in CMAS is limited to the surface area of the ceramic layer.
Comparative example 2
The specific preparation method is basically the same as the embodiment 1, and the difference is that: without addition of SiO 2 And (3) powder. Performing CMAS and CMAS + NaVO 3 And (4) molten salt corrosion test. The results show that the CMAS corrosion penetration distance is about 58 μm, and the CMAS + NaVO 3 The etch penetration distance was about 62 μm.
Comparative example 3
The specific preparation method is basically the same as the embodiment 2, and the differences are as follows: without addition of SiO 2 And (3) powder. Performing CMAS and CMAS + NaVO 3 And (4) molten salt corrosion test. The results show that the CMAS corrosion penetration distance is about 61 μm, and CMAS + NaVO 3 The etch penetration distance was about 64 μm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A molten salt corrosion resistant thermal barrier coating comprising a bond coat and a molten salt corrosion resistant layer; the molten salt corrosion resistant layer is a composite ceramic layer with a layered structure and is formed by mixing YSZ powder and composite oxide powder, wherein the composite oxide powder is formed by Al 2 O 3 And a nucleating agent; in the molten salt corrosion resistant layer, the mass fraction of the composite oxide is 5-15%, and the balance is YSZ.
2. The molten salt corrosion resistant thermal barrier coating of claim 1, wherein the composite oxide powder comprises Al 2 O 3 The mass percentage of the nucleating agent is 90wt.% to 97wt.%, and the rest is the nucleating agent.
3. The molten salt corrosion resistant thermal barrier coating of claim 1, wherein the nucleating agent is SiO 2 、TiO 2 One or more of MgO and CaO.
4. The molten salt corrosion resistant thermal barrier coating of claim 1, wherein the molten salt corrosion resistant layer has a porosity of 5% to 20%.
5. The molten salt corrosion resistant thermal barrier coating of claim 1, wherein the bond coat material is a MCrAlY material system, and the bond coat thickness is 100-150 μm.
6. The molten salt corrosion resistant thermal barrier coating of claim 1, further comprising a first thermal barrier layer; the bonding layer, the first heat insulation layer and the molten salt corrosion resistant layer are sequentially stacked to form a thermal barrier coating;
preferably, the first heat-insulating layer is of a layered structure and is made of other heat-insulating ceramic materials such as YSZ (yttria stabilized zirconia) and rare earth zirconate;
preferably, the thickness of the first heat insulation layer is 100-200 μm, and the deposition thickness of the molten salt corrosion resistant layer is 30-90 μm; and, the first thermal insulation layer and the anti-CMAS and CMAS + NaVO 3 The thickness ratio of the molten salt corrosion layer is 1.5-3.
7. The molten salt corrosion resistant thermal barrier coating of claim 1, wherein an anti-molten salt corrosion layer is formed directly above the bond coat in the thermal barrier coating, and the thickness of the anti-molten salt corrosion layer is 100-300 μm.
8. Method for the production of a molten salt corrosion resistant thermal barrier coating according to any one of claims 1 to 7, characterized in that it comprises the following steps: preparing a bonding layer and an anti-molten salt corrosion layer in a spraying mode;
preferably, the bonding layer is prepared by spraying by any one of low-pressure plasma spraying, vacuum plasma spraying, supersonic flame spraying and cold spraying;
preferably, the molten salt corrosion-resistant layer is prepared by spraying by any one of the methods of atmospheric plasma spraying, vacuum plasma spraying, supersonic plasma spraying and plasma physical vapor deposition.
9. The method of manufacturing according to claim 8, comprising manufacturing the first thermal insulation layer by spraying;
preferably, the first thermal insulation layer is prepared by spraying by any one of the methods of atmospheric plasma spraying, vacuum plasma spraying, supersonic plasma spraying and plasma physical vapor deposition.
10. The method for preparing the ceramic material is characterized in that a bonding layer and an anti-molten salt corrosion layer are sprayed in sequence to form a heat insulation surface layer with a single ceramic structure of a laminated structure;
or, the bonding layer, the first heat-insulating layer with the laminated structure and the molten salt corrosion resistant layer with the laminated structure are sequentially prepared by spraying to form the ceramic heat-insulating surface layer with the double-ceramic structure.
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