CN114032486B - Composite structure thermal protection coating and preparation method thereof - Google Patents

Composite structure thermal protection coating and preparation method thereof Download PDF

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Publication number
CN114032486B
CN114032486B CN202111334070.7A CN202111334070A CN114032486B CN 114032486 B CN114032486 B CN 114032486B CN 202111334070 A CN202111334070 A CN 202111334070A CN 114032486 B CN114032486 B CN 114032486B
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layer
coating
spraying
composite structure
powder
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CN114032486A (en
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郭嘉仪
田伟智
高鑫
杨茗佳
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Beijing Xinghang Electromechanical Equipment Co Ltd
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Beijing Xinghang Electromechanical Equipment Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • 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 composite structure thermal protection coating and a preparation method thereof, belongs to the technical field of surface engineering thermal protection coatings, and solves the problem of lower bonding strength of the composite coating in the prior art. The composite structure thermal protection coating comprises a heat dissipation layer, a coupling agent layer and a heat insulation layer which are sequentially arranged along the direction far away from the surface of a matrix; along the direction far away from the surface of the substrate, the heat dissipation layer sequentially comprises a bonding layer and LaCrO 3 A ceramic layer; the bonding layer is a NiCoCrAlY metal layer; the heat insulating layer is a silicon rubber heat insulating layer. The thermal protection coating provided by the invention has a heat insulation-heat dissipation composite structure, so that the surface temperature of a substrate is reduced, and the bonding strength of the composite structure coating is improved.

Description

Composite structure thermal protection coating and preparation method thereof
Technical Field
The invention relates to the technical field of surface engineering thermal protection coatings, in particular to a thermal protection coating with a composite structure and a preparation method thereof.
Background
In the high-speed flight process of an aircraft, the outer surface can be continuously exposed to a severe aerodynamic heat environment, and the preparation of a heat protection coating on the surface is one of effective methods for reducing the surface temperature of the aircraft and guaranteeing the normal operation of internal products, wherein the coating in the prior art is mainly a heat insulation type or heat dissipation type single-structure coating, the protection effect of a single coating system is limited, and the performance of the coating needs to be further improved along with the improvement of the speed of the aircraft so as to meet the application requirements.
Disclosure of Invention
In view of the above analysis, the embodiments of the present invention aim to provide a thermal protective coating with a composite structure and a preparation method thereof, so as to improve the performance of the thermal protective coating.
On one hand, the invention provides a thermal protection coating with a composite structure, which comprises a heat dissipation layer, a coupling agent layer and a heat insulation layer which are sequentially arranged along the direction far away from the surface of a substrate;
along the direction far away from the surface of the substrate, the heat dissipation layer sequentially comprises a bonding layer and LaCrO 3 A ceramic layer; the bonding layer is a NiCoCrAlY metal layer;
the heat insulation layer is a silicon rubber heat insulation layer.
Further, the coating raw material of the coupling agent layer is a mixture obtained by mixing methyltrimethoxysilane and 120# solvent gasoline according to a mass ratio of 1:20.
Further, the coating raw material silicone rubber base rubber of the silicone rubber heat insulation layer comprises the following components in percentage by mass: crosslinking agent: quick curing agent: gasoline=100, (1.9-2.1): (1.9-2.1): (0-20);
the silicone rubber base rubber is methyl vinyl silicone rubber;
the rapid curing agent is methyltriethoxysilane;
the cross-linking agent is methyltrimethoxysilane.
In another aspect, the present invention provides a method for preparing a thermal protective coating of a composite structure, for preparing the thermal protective coating of a composite structure, the method comprising the steps of:
step 1: preheating a substrate;
step 2: preparing a heat dissipation layer;
firstly spraying NiCoCrAlY powder to form a NiCoCrAlY metal layer as a bonding layer, and then spraying LaCrO 3 Powder formation LaCrO 3 A ceramic layer to obtain a NiCoCrAlY metal layer and LaCrO 3 A heat dissipation layer compounded by the ceramic layers;
step 3: coating a coupling agent on the surface of the heat dissipation layer;
step 4: and brushing the silicon rubber heat insulation layer on the surface of the coupling agent layer to obtain the heat insulation layer.
Further, in the step 1, the surface temperature of the substrate is 80-120 ℃ after the preheating treatment.
Further, in the step 2, a NiCoCrAlY metal layer is obtained by adopting plasma spraying of NiCoCrAlY alloy powder, wherein the particle size of the NiCoCrAlY alloy powder is 15-90 mu m, and the spraying thickness is 0.11-0.12 mm.
Further, in the step 2, the spraying parameters of the NiCoCrAlY powder are as follows: the current is 500-600A, the main air flow is 30-40 NLPM, the powder feeding speed is 3-5 r/min, the spraying distance is 90-110 mm, the spraying speed is 500-600 mm/s, the auxiliary air flow is 1-6 NLPM, and the carrier gas flow is 2-4 NLPM.
Further, in the step 2, the LaCrO 3 The grain diameter of the powder is 15-90 mu m, and the spraying thickness is 0.04-0.09 mm; the LaCrO 3 And drying the powder at 100-120 ℃ for 2-4 hours, and then spraying.
Further, in the step 2, the LaCrO 3 Parameters of powder spraying: the current is 500-600A, the main air flow is 30-40 NLPM, the powder feeding speed is 8-12 r/min, the spraying distance is 90-110 mm, the spraying speed is 500-600 mm/s, the auxiliary air flow is 5-10 NLPM, and the carrier gas flow is 1-3 NLPM.
Further, the main gas is Ar, and the auxiliary gas is H 2 The carrier gas was Ar.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the invention provides a method for reducing the surface temperature of a matrix by combining heat insulation and heat dissipation, and researches on a preparation process method of a heat insulation layer and a heat dissipation layer and matching between the two layers. The obtained composite structure thermal protection coating sequentially comprises the following components along the direction far away from the surface of the substrate: a heat dissipation layer, a coupling agent layer and a heat insulation layer; the heat dissipation layer comprises a NiCoCrAlY metal layer bonding layer and LaCrO 3 A ceramic layer; the heat insulation layer is a silicon rubber heat insulation layer; the emissivity of the heat dissipation layer can reach 0.89, and the heat conductivity of the silicon rubber heat insulation layer is as low as 0.93W/m.k, so that the heat insulation-heat dissipation integrated composite structure coating is obtained.
2. Before the silicon rubber heat-insulating layer is coated, the coupling agent layer is prepared, si-N bonds in the coupling agent react with water adsorbed on the surface of the high-emissivity heat-radiating coating on one hand, and participate in the crosslinking reaction of the silicon rubber heat-insulating layer on the other hand, so that the silicon rubber heat-insulating layer and the high-emissivity heat-radiating layer are effectively combined.
3. The invention obtains the thermal protection coating with a composite structure, the total thickness is 1.67-1.94 mm, wherein the thickness of the bonding layer of the NiCoCrAlY metal layer is 0.11-0.12 mm, and the thickness of the LaCrO metal layer is 0.11-0.12 mm 3 The ceramic layer is 0.04-0.09 mm, the coupling agent layer is 0.01-0.03 mm, and the thickness of the silicon rubber heat insulation layer is 1.5-1.7 mm. The emissivity of the heat dissipation layer is 0.86-0.89, the thermal conductivity of the silicon rubber heat insulation layer is 0.93-0.98W (m.k), and the bonding strength is 34-36 MPa.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is a schematic illustration of a composite thermal protective coating according to the present invention;
FIG. 2a is a first microstructure of a high emissivity thermal release coating made in accordance with example 1 of the present invention;
FIG. 2b is a second microstructure of the high emissivity thermal release coating made in example 1 of the present invention;
fig. 3 is a comparative graph of the composite structure thermal protective coating structure prepared in example 1 of the present invention and the composite structure thermal protective coating structure prepared in comparative example.
Reference numerals:
1-a substrate; 2-a heat dissipation layer; a 3-coupling agent layer; 4-heat insulation layer.
Detailed Description
Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and together with the description serve to explain the principles of the invention, and are not intended to limit the scope of the invention.
In one aspect, the invention discloses a thermal protective coating of a composite structure, as shown in fig. 1, along the direction away from the surface of a substrate, the coating sequentially comprises: a heat dissipation layer, a coupling agent layer and a heat insulation layer;
the heat dissipation layer comprises a NiCoCrAlY metal bonding layer and LaCrO 3 A ceramic layer;
the heat insulation layer is a silicon rubber heat insulation layer.
Further, the coating raw materials of the coupling agent layer are obtained by diluting methyltrimethoxysilane and 120# solvent gasoline according to the proportion of 1:20; the cross-linking agent is.
Further, the coating raw material silicone rubber base rubber of the silicone rubber heat insulation layer comprises the following components in percentage by mass: crosslinking agent: quick curing agent: gasoline=100, (1.9-2.1): (1.9-2.1): (0-20).
Wherein the silicone rubber base rubber is methyl vinyl silicone rubber; the fast curing agent is methyltriethoxysilane.
On the other hand, the invention discloses a preparation method of a thermal protection coating with a composite structure, which comprises the following steps:
step 1: preheating treatment of substrate
Clamping a substrate to be sprayed on a tool, starting a spraying system, and preheating the substrate after flame flow is stable;
step 2: preparation of heat dissipation layer
Firstly spraying NiCoCrAlY powder to form a NiCoCrAlY metal layer as a bonding layer, and then spraying LaCrO 3 Powder formation LaCrO 3 A ceramic layer to obtain a NiCoCrAlY metal layer and LaCrO 3 A heat dissipation layer compounded by the ceramic layers;
step 3: coupling agent coating
Coating a coupling agent on the surface of the heat dissipation layer;
step 4: thermal barrier coating
And brushing the silicon rubber heat insulation layer on the surface of the coupling agent layer to obtain the heat insulation layer.
Specifically, in the step 1, the substrate is preheated to a surface temperature of 80-120 ℃.
Specifically, in the step 2, a NiCoCrAlY metal layer is obtained by adopting plasma spraying, the particle size of the NiCoCrAlY alloy powder is 15-90 mu m, such as 18-53 mu m, and the spraying thickness is 0.11-0.12 mm; with plasma spraying, too large or too small particle sizes affect the degree of powder melting, eventually leading to increased internal defects in the coating.
Specifically, in the step 2, plasma spraying LaCrO is adopted 3 Powder, laCrO 3 The grain diameter of the powder is 15-90 mu m, and the spraying thickness is 0.04-0.09 mm; the powder is dried for 2 to 4 hours at the temperature of 100 to 120 ℃ and then sprayed.
Considering LaCrO 3 The powder is easy to absorb moisture in the air, and can cause LaCrO 3 Powder flowability is poor; thus, laCrO is added before spraying 3 The powder is dried for 2 to 4 hours at the temperature of 100 to 120 ℃, the moisture in the powder is removed, and the powder is sufficiently dried to improve the fluidity in the powder spraying process.
Specifically, in the step 2, in the plasma spraying process, the main gas is Ar, and the auxiliary gas is H 2 The carrier gas was Ar. The main gas generates plasma, the auxiliary gas increases the enthalpy value, and the carrier gas sends the powder material into the plasma jet.
Specifically, in the step 2, the spraying parameters of the NiCoCrAlY powder are as follows: the current is 500-600A, the main air flow is 30-40 NLPM, the powder feeding speed is 3-5 r/min, the spraying distance is 90-110 mm, the spraying speed is 500-600 mm/s, the auxiliary air flow is 1-6 NLPM, the carrier gas flow is 2-4 NLPM, and the spraying thickness is 0.11-0.12 mm.
Preparing a metal bonding layer on the substrate treated in the step 1 by adopting an atmospheric plasma spraying process; the metal bonding layer is a NiCoCrAlY metal layer, has good thermal expansion coefficient matching property with the metal matrix, and plays a role in the metal matrix and LaCrO 3 Transition of the ceramic layer.
Specifically, in the step 2, the LaCrO 3 Parameters of powder spraying: the current is 500-600A, the main air flow is 30-40 NLPM, the powder feeding speed is 8-12 r/min, the spraying distance is 90-110 mm, the spraying speed is 500-600 mm/s, the auxiliary air flow is 5-10 NLPM, the carrier gas flow is 1-3 NLPM, and the spraying thickness is 0.04-0.09 mm.
In the research, the phenomenon that the adhesion is unstable easily occurs when the silicon rubber heat insulation layer is directly prepared on the surface of the heat dissipation layer. In order to improve the activity of the surface of the high-emissivity heat dissipation layer, the binding force between the high-emissivity heat dissipation layer and the silicon rubber heat insulation layer is increased, a layer of coupling agent is applied before the silicon rubber heat insulation layer is coated, and the effective binding between the silicon rubber heat insulation layer and the heat dissipation layer is realized through the coupling agent.
The coupling agent is formed by diluting methyltrimethoxysilane with 120# solvent gasoline according to the mass ratio of 1:20.
The invention realizes the effective combination between the silicon rubber heat insulation layer and the heat dissipation layer through the coupling agent, and solves the problem of the reduction of the surface energy of the heat dissipation layer with high emissivity. The heat dissipation layer obtained by the method is a heat dissipation coating with high emissivity, is a multi-element composite material layer prepared by high-temperature plasma spraying, and is characterized in that working gas is argon (Ar) when the heat dissipation coating with high emissivity is prepared, oxygen deficiency is easily caused on the surface of the coating by spraying in an argon environment, and oxygen vacancies are formed (namely molecules on the surface of the coating lack a chemical bond). Therefore, the dangling bond of the high-emissivity heat dissipation layer is mainly an oxygen vacancy, and the special porous structure of the dangling bond is added, so that the high-emissivity heat dissipation coating is high in surface activity and strong in adsorption capacity. The water molecules enter the surface of the coating layer and have concentration gradient diffusion, flow along micropores of the surface of the coating layer, capillary flow and other modes, and the water molecules in the air gradually occupy oxygen vacancies, so that the surface energy of the high-emissivity heat-dissipation coating layer is reduced, and the phenomenon of infirm adhesion easily occurs when the silicon rubber heat-insulation layer is directly prepared on the surface of the high-emissivity heat-dissipation layer.
In addition, the silicon rubber heat insulation layer consists of methyl vinyl silicon rubber base rubber, a cross-linking agent and a rapid curing agent. Wherein, the silicon rubber base rubber takes a Si-O chain link as a basic structural unit, and the end silicon hydroxyl (Si-OH) provides reactivity.
The Si-N bond contained in the methyltrimethoxysilane in the coupling agent can be subjected to chemical bonding reaction with Si-OH on the surface of the substrate and the methyl vinyl silicone rubber base rubber to form covalent bond; methyltriethoxysilane contains a siloxane group (Si-OR) and can undergo a chemical bonding reaction with the Si-OH of the methyl vinyl silicone rubber to form a covalent bond. The coupling agent is prepared by diluting methyltrimethoxysilane by adding 120# solvent gasoline according to the mass ratio of 1:20, and then diluting, so that the coupling agent is easier to permeate into pores of a high-emissivity heat-dissipating coating. The Si-N bond in the methyltrimethoxysilane of the coupling agent can react with water adsorbed on the surface of the high-emissivity heat-dissipation coating, and participate in the crosslinking reaction of the silicon rubber heat-insulation layer, so that the effect of improving the bonding strength is achieved, and the effective combination between the silicon rubber heat-insulation layer and the heat-dissipation layer is realized.
In the coupling agent and the silicon rubber heat insulation layer, the 120# solvent gasoline not only ensures that methyltrimethoxysilane is better dissolved and the fluidity and the penetrability of the methyltrimethoxysilane are increased, but also has extremely strong volatility, so that the coating is quickly cured after being coated.
Specifically, in the step 3, the coupling agent layer is coated with one or more layers by adopting a normal temperature spraying method, the heat dissipation layer is completely covered, the coating thickness is 0.01-0.03 mm, and the heat insulation layer is continuously coated after the drying time is 0.5-1 h.
Specifically, in the step 4, a normal temperature brushing process is adopted to brush the silicon rubber heat insulation layer on the surface of the coupling agent layer, so that the thickness of the heat insulation layer is 1.5-1.7 mm. The coating raw materials of the silicon rubber heat insulation layer are as follows by mass ratio: silicone rubber base rubber: crosslinking agent: quick curing agent: gasoline=100, (1.9-2.1): (1.9-2.1): (0-20). Preferably, the silicone rubber base rubber is methyl vinyl silicone rubber, the cross-linking agent is methyl trimethoxy silane, the quick curing agent is methyl triethoxy silane, and the gasoline is 120# gasoline. Illustratively, methyl vinyl silicone rubber: methyltrimethoxysilane: methyltriethoxysilane: 120# gasoline = 100:1.9:1.9:10, or, methyl vinyl silicone rubber: methyltrimethoxysilane: methyltriethoxysilane: 120# gasoline = 100:2.1:2.1:20, or, methyl vinyl silicone rubber: methyltrimethoxysilane: methyltriethoxysilane: 120# gasoline = 100:1.9:1.9:15.
Specifically, in the step 4, the total thickness of the obtained composite structure thermal protection coating is 1.6-2 mm, the emissivity of the coating is more than or equal to 0.85, the thermal conductivity is less than or equal to 1W (m.k), and the bonding strength is more than or equal to 30MPa.
The thermal protection coating with the composite structure is obtained by 3 embodiments of the invention, the total thickness is 1.67-1.94 mm, wherein the thickness of the NiCoCrAlY metal bonding layer is 0.11-0.12 mm, and the thickness of the LaCrO metal bonding layer is 0.11-0.12 mm 3 The ceramic layer is 0.04-0.09 mm, the coupling agent layer is 0.01-0.03 mm, and the thickness of the silicon rubber heat insulation layer is 1.5-1.7 mm. The emissivity of the heat dissipation layer is 0.86-0.89, the thermal conductivity of the silicon rubber heat insulation layer is 0.93-0.98W (m.k), and the bonding strength is 34-36 MPa.
Example 1
The embodiment provides a preparation method of a composite structure heat protection coating, and the composite structure heat protection coating is obtained by adopting the method, and the specific details are as follows:
s1: powder pretreatment for spraying
Screening LaCrO with particle size of 15 μm 3 The powder was placed in a clean tray, then placed in an oven at 100 ℃ for 4 hours and loaded into a powder feeder.
S2: preparation of heat dissipation layer
And (3) clamping the stainless steel substrate sample to be sprayed on a tool, starting a spraying system, and preheating the stainless steel substrate for 1 time after flame flow is stable, wherein the preheating temperature is 90 ℃.
S3: and (3) spraying NiCoCrAlY powder by adopting a plasma spraying technology to form a NiCoCrAlY metal layer as a bonding layer, wherein the spraying parameters are as follows: the particle size of the NiCoCrAlY powder is 15 mu m, the current is 600A, the main air flow is 40NLPM, the powder feeding speed is 5r/min, the spraying distance is 110mm, the spraying speed is 600mm/s, the auxiliary air flow is 6NLPM, the carrier air flow is 4NLPM, and the spraying thickness is 0.12mm.
Wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
S4: laCrO is carried out by a powder feeding device 3 The powder is fed into the flame flow, and after the flame flow is stabilized, laCrO is carried out 3 Preparation of ceramic layer, laCrO 3 The particle size of the powder is 15-90 mu m, and the plasma spraying process parameters are as follows: the current is 600A, the main air flow is 40NLPM, the powder feeding speed is 12r/min, the spraying distance is 110mm, the spraying speed is 600mm/s, the auxiliary air flow is 10NLPM, the carrier gas flow is 3NLPM, and the spraying thickness is 0.04mm.
Wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
And obtaining the heat dissipation coating with high emissivity.
S5: coupling agent coating
And diluting the methyltrimethoxysilane and the 120# solvent gasoline according to the mass ratio of 1:20, and then diluting to obtain the coupling agent, and coating the coupling agent on the surface of the high-emissivity layer, wherein the coating thickness is 0.01mm.
S6: thermal barrier coating
The silicon rubber heat insulation layer is prepared from methyl vinyl silicon rubber by mass ratio: methyltrimethoxysilane: methyltriethoxysilane: the 120# gasoline=100:2.1:2.1:20 is prepared into a coating, and the coating is prepared on the surface of the coupling agent layer by adopting a normal-temperature brush coating process, so that the heat insulation layer is obtained, and the thickness is 1.5mm.
The composite structural thermal protective coating obtained in example 1 had a total thickness of 1.67mm, wherein the NiCoCrAlY metal layer had a bond coat thickness of 0.12mm and LaCrO 3 The ceramic layer is 0.04mm, the coupling agent layer is 0.01mm, and the thickness of the heat insulation layer is 1.5mm.
The emissivity of the heat dissipation layer is 0.86, the thermal conductivity of the heat insulation layer is 0.98W (m.k), and the bonding strength is 36MPa.
Example 2
The embodiment provides a preparation method of a composite structure heat protection coating, and the composite structure heat protection coating is obtained by adopting the method, and the specific details are as follows:
s1: powder pretreatment for spraying
Screening LaCrO with particle size of 50 μm 3 The powder was placed in a clean tray, then placed in an oven at 120 ℃ for 2.5 hours and loaded into a powder feeder.
S2: preparation of heat dissipation layer
And (3) clamping the stainless steel substrate sample to be sprayed on a tool, starting a spraying system, and preheating the stainless steel substrate for 1 time after flame flow is stable, wherein the preheating temperature is 100 ℃.
S3: and (3) spraying NiCoCrAlY powder by adopting a plasma spraying technology to form a NiCoCrAlY metal layer as a bonding layer, wherein the spraying parameters are as follows: the particle size of the NiCoCrAlY powder is 50 mu m, the current is 500A, the main air flow is 30NLPM, the powder feeding speed is 3r/min, the spraying distance is 90mm, the spraying speed is 500mm/s, the auxiliary air flow is 1NLPM, the carrier gas flow is 2NLPM, and the spraying thickness is 0.11mm.
Wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
S4: laCrO is carried out by a powder feeding device 3 The powder is fed into the flame flow, and after the flame flow is stabilized, laCrO is carried out 3 Preparation of ceramic layer, laCrO 3 The particle size of the powder is 15-90 mu m, and the plasma spraying process parameters are as follows: the current is 500A, the main air flow is 30NLPM, the powder feeding speed is 8r/min, the spraying distance is 90mm, the spraying speed is 500mm/s, the auxiliary air flow is 5NLPM, and the carrier gas flow is 1NLPM.
Wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
And obtaining the heat dissipation coating with high emissivity.
S5: coupling agent coating
And diluting methyltrimethoxysilane and 120# solvent gasoline according to the mass ratio of 1:20 to obtain the coupling agent, and coating the coupling agent on the surface of the heat dissipation layer with the coating thickness of 0.02mm.
S6: thermal barrier coating
The silicon rubber heat insulation layer is prepared from methyl vinyl silicon rubber by mass ratio: methyltrimethoxysilane: methyltriethoxysilane: the 120# gasoline=100:1.9:1.9:10 prepared coating is prepared on the surface of the coupling agent layer by adopting a normal-temperature brush coating process, and the heat insulation layer is obtained with the thickness of 1.66mm.
Finally, the thermal protection coating with the composite structure is obtained.
Example 2A composite thermal protective coating was obtained having a total thickness of 1.85mm, wherein the NiCoCrAlY metal layer had a tie layer thickness of 0.11mm and LaCrO 3 The ceramic layer is 0.06mm, the thickness of the coupling agent layer is 0.02mm, and the thickness of the silicon rubber heat insulation layer is 1.66mm.
The emissivity of the heat dissipation layer is 0.89, the thermal conductivity of the heat insulation layer is 0.95W (m.k), and the bonding strength is 35MPa.
Example 3
The embodiment provides a preparation method of a composite structure heat protection coating, and the composite structure heat protection coating is obtained by adopting the method, and the specific details are as follows:
s1: powder pretreatment for spraying
LaCrO with particle size of 90 μm is selected 3 The powder was placed in a clean tray, then placed in an oven at 110 ℃ for 2 hours and loaded into a powder feeder.
S2: preparation of heat dissipation layer coating
And (3) clamping the stainless steel substrate sample to be sprayed on a tool, starting a spraying system, and preheating the stainless steel substrate for 1 time after flame flow is stable, wherein the preheating temperature is 120 ℃.
S3: and (3) spraying NiCoCrAlY powder by adopting a plasma spraying technology to form a NiCoCrAlY metal layer as a bonding layer, wherein the spraying parameters are as follows: the particle size of the NiCoCrAlY powder is 90 mu m, the current is 550A, the main air flow is 35NLPM, the powder feeding speed is 4r/min, the spraying distance is 100mm, the spraying speed is 550mm/s, the auxiliary air flow is 4NLPM, the carrier air flow is 3NLPM, and the spraying thickness is 0.12mm.
Wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
S4: laCrO is carried out by a powder feeding device 3 The powder is fed into the flame flow, and after the flame flow is stabilized, laCrO is carried out 3 Preparation of ceramic layer, laCrO 3 The particle size of the powder is 15-90 mu m, and the plasma spraying process parameters are as follows: the current is 550A, the main air flow is 35NLPM, the powder feeding speed is 10r/min, the spraying distance is 100mm, the spraying speed is 550mm/s, the auxiliary air flow is 8NLPM, the carrier gas flow is 2NLPM, and the spraying thickness is 0.09mm.
Wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
And obtaining the heat dissipation coating with high emissivity.
S5: coupling agent coating
And diluting methyltrimethoxysilane and 120# solvent gasoline according to the ratio of 1:20 to obtain the coupling agent, and coating the coupling agent on the surface of the heat dissipation layer, wherein the coating thickness is 0.03mm.
S6: thermal barrier coating
The silicon rubber heat insulation layer is prepared from methyl vinyl silicon rubber by mass ratio: methyltrimethoxysilane: methyltriethoxysilane: the 120# gasoline=100:1.9:1.9:15 is prepared into a coating, and the coating is prepared on the surface of the coupling agent layer by adopting a normal-temperature brush coating process, so that the heat insulation layer is obtained, and the thickness is 1.7mm.
Finally, the thermal protection coating with the composite structure is obtained.
Example 3A composite thermal protective coating was obtained having a total thickness of 1.94mm, wherein the NiCoCrAlY metal layer had a tie layer thickness of 0.12mm and LaCrO 3 The ceramic layer is 0.09mm, the coupling agent layer is 0.03mm, and the thickness of the heat insulation layer is 1.7mm.
The emissivity of the heat dissipation layer is 0.87, the thermal conductivity of the heat insulation layer is 0.93W (m.k), and the bonding strength is 34MPa.
Comparative example
This comparative example provides a method for preparing a thermal protective coating of a composite structure without a coupling agent, other specific details are the same as those of example 1, and the thermal protective coating of a composite structure obtained by the method of comparative example is compared with the thermal protective coating of a composite structure obtained in example 1. As shown in fig. 3.
The coating obtained in the comparative example has a total thickness of 1.83mm, wherein the NiCoCrAlY metal layer has a bonding layer thickness of 0.11mm and LaCrO 3 The ceramic layer is 0.06mm, and the thickness of the heat insulation layer is 1.66mm.
The test shows that the emissivity of the heat dissipation layer is 0.88, the thermal conductivity of the heat insulation layer is 0.94W (m.k), the bonding strength is 12MPa, and the bonding strength does not meet the working condition use requirement (generally, the working condition use requirement is that the bonding strength is more than or equal to 25 MPa).
The composite structure thermal protection coating obtained by the method of the comparative example is compared with the composite structure thermal protection coating obtained by the example 1 after the coating is tested by a cross-hatch adhesion test method. As shown in fig. 3: the left square frame is a coating obtained by a comparative example without the coupling agent, the right square frame is a coating obtained by example 1 with the coupling agent, and it can be seen that the silicon rubber heat insulation layer in the area coated with the coupling agent cannot be completely separated from the heat dissipation layer, the silicon rubber heat insulation layer in the area not coated with the coupling agent can be separated from the heat dissipation layer, and almost no silicon rubber heat insulation layer remains on the substrate.
The coatings obtained in examples 1 to 3 and comparative example were subjected to comparison of test data, and the comparison results are shown in table 1:
table 1 comparison of test result data for examples 1 to 3 with comparative example
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims (7)

1. The preparation method of the composite structure thermal protection coating is characterized in that the composite structure thermal protection coating comprises a heat dissipation layer, a coupling agent layer and a heat insulation layer which are sequentially arranged along the direction far away from the surface of a substrate;
along the direction far away from the surface of the substrate, the heat dissipation layer sequentially comprises a bonding layer and LaCrO 3 A ceramic layer; the bonding layer is a NiCoCrAlY metal layer;
the heat insulation layer is a silicon rubber heat insulation layer;
the coating raw material of the coupling agent layer is a mixture obtained by mixing methyltrimethoxysilane and 120# solvent gasoline according to the mass ratio of 1:20;
the coating raw material silicone rubber base rubber of the silicone rubber heat insulation layer comprises the following components in percentage by mass: crosslinking agent: quick curing agent: gasoline=100, (1.9-2.1): (1.9-2.1): (0-20);
the silicone rubber base rubber is methyl vinyl silicone rubber;
the rapid curing agent is methyltriethoxysilane;
the cross-linking agent is methyltrimethoxysilane;
the thickness of the NiCoCrAlY metal layer is 0.11 mm-0.12 mm, and the LaCrO 3 Thickness of ceramic layerThe degree is 0.04 mm-0.09 mm, the thickness of the coupling agent layer is 0.01 mm-0.03 mm, and the thickness of the silicon rubber heat insulation layer is 1.5 mm-1.7 mm;
the preparation method comprises the following steps:
step 1: preheating a substrate;
step 2: preparing a heat dissipation layer;
firstly spraying NiCoCrAlY powder to form a NiCoCrAlY metal layer as a bonding layer, and then spraying LaCrO 3 Powder formation LaCrO 3 A ceramic layer to obtain a NiCoCrAlY metal layer and LaCrO 3 A heat dissipation layer compounded by the ceramic layers;
step 3: coating a coupling agent on the surface of the heat dissipation layer;
step 4: and brushing the silicon rubber heat insulation layer on the surface of the coupling agent layer to obtain the heat insulation layer.
2. The method for preparing a thermal protective coating with a composite structure according to claim 1, wherein in the step 1, the surface temperature of the substrate is 80 ℃ to 120 ℃ after the preheating treatment.
3. The method for preparing the thermal protective coating with the composite structure according to claim 1, wherein in the step 2, a NiCoCrAlY metal layer is obtained by adopting plasma spraying NiCoCrAlY alloy powder, and the particle size of the NiCoCrAlY alloy powder is 15-90 μm.
4. The method for preparing a thermal protective coating for a composite structure according to claim 1, wherein in the step 2, the NiCoCrAlY powder is sprayed with parameters: the current is 500-600A, the main air flow is 30-40 NLPM, the powder feeding speed is 3-5 r/min, the spraying distance is 90-110 mm, the spraying speed is 500-600 mm/s, the auxiliary air flow is 1-6 NLPM, and the carrier gas flow is 2-4 NLPM.
5. The method for preparing a thermal protective coating of a composite structure according to claim 1, wherein in the step 2, the LaCrO is 3 The particle size of the powder is 15-90 mu m; the LaCrO 3 Drying the powder at 100-120 DEG CAnd spraying after 2-4 hours.
6. The method for preparing a thermal protective coating of a composite structure according to claim 1, wherein in the step 2, the LaCrO is 3 Parameters of powder spraying: the current is 500-600A, the main air flow is 30-40 NLPM, the powder feeding speed is 8-12 r/min, the spraying distance is 90-110 mm, the spraying speed is 500-600 mm/s, the auxiliary air flow is 5-10 NLPM, and the carrier gas flow is 1-3 NLPM.
7. The method for preparing a thermal protective coating of a composite structure according to claim 4 or 6, wherein the main gas is Ar and the auxiliary gas is H 2 The carrier gas was Ar.
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