CN110653136A - Surface oxidation-resistant high-emissivity coating of porous fibrous carbon-based heat-insulating material and preparation method thereof - Google Patents

Surface oxidation-resistant high-emissivity coating of porous fibrous carbon-based heat-insulating material and preparation method thereof Download PDF

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CN110653136A
CN110653136A CN201910953324.XA CN201910953324A CN110653136A CN 110653136 A CN110653136 A CN 110653136A CN 201910953324 A CN201910953324 A CN 201910953324A CN 110653136 A CN110653136 A CN 110653136A
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coating
emissivity
mass
silicon
layer
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CN110653136B (en
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高宇智
张凡
李健
李文静
杨洁颖
赵英民
张昊
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Aerospace Research Institute of Materials and Processing Technology
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    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • 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
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/582—No clear coat specified all layers being cured or baked together

Abstract

The invention discloses a surface oxidation-resistant high-emissivity coating based on a porous fibrous carbon-based heat-insulating material and a preparation method thereof. The coating comprises an inner layer transition coating, a middle layer oxidation resistant coating and a surface layer high emissivity coating; the inner layer transition coating comprises 35-55% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 41-63% of high-emissivity insoluble metal silicide; the middle anti-oxidation coating comprises 50-70% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 26-48% of high-emissivity insoluble metal silicide; the surface high emissivity coating comprises: 30-40% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 56-68% of high-emissivity insoluble metal silicide. The coating is connected with the base material through the transition layer, so that the interface bonding force of the coating and the base is improved, the problem that the thermal expansion coefficients of the coating and the base are not matched is solved, and the surface heat insulation prevention requirement of a space or an adjacent space aircraft can be met.

Description

Surface oxidation-resistant high-emissivity coating of porous fibrous carbon-based heat-insulating material and preparation method thereof
Technical Field
The invention belongs to the field of preparation of heat-proof materials, and particularly relates to a surface oxidation-resistant high-emissivity coating based on a porous fibrous carbon-based heat-proof material and a preparation method thereof.
Background
With the continuous improvement of the flying speed of the aircraft, the material which can still play the role of prevention and heat insulation in the extremely severe pneumatic environment is one of the key factors for ensuring the service performance and the service life of the new-generation aircraft. At present, the excellent performance of the carbon-based heat insulation material such as low density and high temperature resistance becomes one of the key research directions of the heat protection materials for aerospace at present. However, the carbon-based material is very easy to be oxidized and lose efficacy in a high-temperature aerobic environment, and the application of the carbon-based material in the field of aerospace thermal protection materials is limited. The anti-oxidation high-emissivity coating prepared on the surface of the carbon-based heat-insulating material can effectively solve the problem that the carbon-based material is easy to lose efficacy in a high-temperature aerobic environment, and the surface heat is quickly radiated by utilizing the high-emissivity component on the surface, so that the anti-oxidation high-emissivity coating has important significance for improving the temperature resistance and the protective performance of the thermal protective material.
The Chinese invention patent CN106673709B provides a preparation method of a silicide-glass hybrid coating which is used on the surface of a porous heat-insulating material, can be used in an environment with the temperature of 1500 ℃ at most and has the characteristic of high emissivity. The coating is suitable for coating with single proportion, and is suitable for the surface of porous fibrous zirconia ceramic or porous fibrous mullite ceramic. However, with the application of the carbon-based heat-insulating material with more excellent temperature resistance in the field of thermal protection, the prepared coating which has excellent adaptability with the fibrous carbon-based heat-insulating material, stronger binding force between the coating and the matrix and the function of isolating the carbon-based heat-insulating material from oxygen components in the environment is of great importance for further increasing the service temperature of the heat-protecting material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the anti-oxidation high-emissivity coating on the surface of the porous fibrous carbon-based heat-insulating material is provided, so that the anti-heat-insulating requirement on the surface of a space or an adjacent space aircraft can be met.
The technical scheme of the invention is as follows:
a surface oxidation-resistant high-emissivity coating of a porous fibrous carbon-based heat-insulating material comprises an inner-layer transition coating, a middle-layer oxidation-resistant coating and a surface-layer high-emissivity coating; the inner transition coating comprises the following components in percentage by mass: 35-55% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 41-63% of high-emissivity insoluble metal silicide; the middle anti-oxidation coating comprises the following components in percentage by mass: 50-70% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 26-48% of high-emissivity insoluble metal silicide; the surface layer high-emissivity coating comprises the following components in percentage by mass: 30-40% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 56-68% of high-emissivity insoluble metal silicide.
Further, the glass comprises the following components in percentage by mass: 75-90% silica and 10-25% boron oxide.
Further, the high-emissivity refractory metal silicide comprises one or two of molybdenum disilicide, tantalum disilicide and tungsten disilicide.
Further, the inner transition coating penetrates into the base material by 1-2mm, the thickness of the middle oxidation resistant coating is 100-.
Furthermore, the temperature emissivity of the coating in the wavelength range of 1.3-2.5 μm is greater than 0.85 and the highest can be greater than 0.91, the binding force between the coating and the substrate is greater than or equal to 4MPa, the weight loss rate is less than or equal to 12 percent in 1300-1550 ℃ high-temperature aerobic environment, the minimum weight loss rate at 1550 ℃ is less than or equal to 8.5 percent, and the oxyacetylene ablation rate at 1600 ℃ is 0.2-0.5 mm.
A preparation method of an oxidation-resistant high-emissivity coating on the surface of a porous fibrous carbon-based heat-insulating material comprises the following specific steps:
(1) preparing glass powder: weighing 75-90% of silicon dioxide and 10-25% of boron oxide powder by mass percent, ball-milling and mixing in a mixing tank, then placing in a 1300-1400 ℃ furnace for heat preservation for 2-4 hours, taking out, cooling in air to obtain glass frit, vibrating and crushing and grinding into powder for later use;
(2) preparing an inner layer transition coating: weighing 35-55% by mass of glass powder, 2-4% by mass of one or two of silicon hexaboride powder and silicon tetraboride and 41-63% by mass of one or two of molybdenum disilicide and tantalum disilicide, and performing ball-milling mixing treatment by taking absolute ethyl alcohol as a solution without adding a dispersing agent to obtain inner layer transition layer slurry;
(3) uniformly brushing the slurry uniformly mixed in the step (2) on the surface of the carbon-based heat-insulating material;
(4) preparing a middle-layer antioxidant coating: weighing 50-70% by mass of glass powder, 2-4% by mass of one or two of silicon hexaboride and silicon tetraboride powder, and 26-48% by mass of one or two of molybdenum disilicide and tantalum disilicide powder, and performing ball-milling mixing treatment by taking absolute ethyl alcohol as a solution to obtain middle-layer antioxidation layer slurry;
(5) uniformly spraying the slurry uniformly mixed in the step (4) on the surface of a matrix;
(6) preparing a surface high-emissivity coating: weighing 30-40% by mass of glass powder, 2-4% by mass of one or two of silicon hexaboride powder and silicon tetraboride and 56-68% by mass of one or two of molybdenum disilicide and tantalum disilicide, and performing ball-milling mixing treatment by taking absolute ethyl alcohol as a solution to obtain surface layer antioxidation layer slurry;
(7) uniformly spraying the uniformly mixed slurry obtained in the step (6) on the surface of a matrix;
(8) drying the coating and the substrate, then placing the coating and the substrate in an inert atmosphere for heat treatment, keeping the temperature for 20-30min after the temperature reaches 1250-.
Preferably, in the step (1), the molten glass is pulverized so that the particle diameter of the glass powder is in the range of 5 to 10 μm.
Preferably, the mass ratio of the absolute ethyl alcohol to the raw materials in the steps (2), (4) and (6) is 1: 0.5-1.5.
Preferably, the ball milling mixing parameters of the steps (2), (4) and (6) are as follows: ball milling is carried out for 2-4 hours at the rotating speed of 200rpm of 180-.
Preferably, in step (3), the transition layer coating penetrates into the base material to a thickness of about 1 to 2 mm.
Preferably, in step (5), the anti-oxidation layer coating is sprayed on the surface of the substrate, and the thickness is 100-300 μm.
Preferably, in step (7), the high emissivity coating is sprayed on the surface of the substrate to a thickness of 100 and 200 μm.
Preferably, in the steps (5) and (7), the discharge amount of compressed high-purity nitrogen gas used for spraying is 25-30L/min.
Preferably, in step (8), after the coating is prepared, the coating needs to be dried at room temperature for 8 hours, then dried in an oven at 70 ℃ for 8 hours, and dried in an oven at 130 ℃ for 2 hours.
The anti-oxidation high-emissivity coating prepared by the method has the temperature emissivity of more than 0.85 in the wavelength range of 1.3-2.5 mu m, the highest emissivity of more than 0.91 in the range, the binding force between the coating and a substrate is more than or equal to 4MPa, the weight loss rate is less than or equal to 12 percent in a 1300-1550 ℃ high-temperature aerobic environment, the lowest weight loss rate is less than or equal to 8.5 percent at 1550 ℃, and the oxyacetylene ablation rate is 0.2-0.5mm at 1600 ℃.
Has the advantages that:
(1) gradient design of coating components, namely 1) penetrating into the surface of a substrate to form a transition coating with 1-2mm thickness and good bonding property with a carbon-based heat-insulating material and small expansion deformation at high temperature in an inner layer, enhancing the bonding force of the surface coating and the substrate, and buffering the damage caused by the inconsistent expansion coefficients of the coating and the substrate material in a high-temperature environment; 2) the middle layer is a compact anti-oxidation coating, effectively prevents oxygen diffusion channels under high temperature conditions, and has the functions of resisting heat flow impact and keeping structural stability; 3) and finally, forming a high-emissivity heat-proof coating on the surface layer, and quickly radiating the surface heat storage capacity. The coating and the substrate have good interface binding force, the binding force between the coating and the substrate is more than or equal to 4MPa, the strong binding force between the coating and the substrate is ensured, and the coating is not easy to peel off in a severe power environment; meanwhile, the coating has good temperature resistance and oxidation resistance, the weight loss rate is less than or equal to 15 percent in a 1300-1500 ℃ high-temperature aerobic environment, and the ablation rate of oxyacetylene at 1600 ℃ is 0.2-0.5 mm; in addition, the coating has high emissivity, the room temperature emissivity is more than 0.85 in the wavelength range of 1.3-2.5 mu m, the highest emissivity in the range is more than 0.91, the surface heat of the material can be rapidly radiated, and the surface heat protection requirement of the aerospace craft is met.
(2) The coating slurry has moderate particle size and viscosity, can meet the requirements of brushing and slurry spraying, and has controllable coating thickness, uniform slurry and easy operation.
Drawings
FIG. 1 is a graph of a sample of the porous fibrous carbon-based thermal insulation material and surface oxidation resistant high emissivity coating made in example 3.
FIG. 2 is an emissivity of the oxidation resistant high emissivity coating made in example 3 over a wavelength range of 1.3-2.5 μm.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
(1) Preparing glass powder: weighing 75% of silicon dioxide and 25% of boron oxide powder by mass, ball-milling and mixing in a mixing tank, then placing in a 1300 ℃ furnace for heat preservation for 2 hours, taking out and quenching to obtain a glass frit, vibrating and crushing the frit, and grinding the frit into powder for later use;
(2) preparing an inner layer transition coating: weighing 35% of glass powder, 2% of silicon hexaboride powder and 41% of molybdenum disilicide according to mass percent, and taking absolute ethyl alcohol as a solution, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 1: 1.5. And carrying out ball milling and mixing treatment for 4h by using a star ball mill at the rotating speed of 180rpm to obtain inner-layer transition layer slurry. Uniformly brushing the slurry on the surface of the carbon-based heat-insulating material to form a coating layer which penetrates into the matrix to a depth of 2 mm;
(3) preparing a middle-layer antioxidant coating: weighing glass powder with the mass percent of 70%, silicon hexaboride with the mass percent of 4%, molybdenum disilicide with the mass percent of 14% and tantalum disilicide powder with the mass percent of 12%, taking absolute ethyl alcohol as a solution, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 1: 0.8, and carrying out ball-milling mixing treatment for 3 hours by using a star-type ball mill at the rotating speed of 180 rpm. Spraying the slurry on the transition layer on the surface of the substrate by utilizing compressed high-purity nitrogen at the displacement of 25-30L/min;
(4) preparing a surface high-emissivity coating: weighing 30 mass percent of glass powder, 4 mass percent of silicon hexaboride powder, 24 mass percent of molybdenum disilicide and 42 mass percent of tantalum disilicide, and carrying out ball-milling mixing treatment for 2 hours by using a star-type ball mill at the rotating speed of 200rpm, wherein absolute ethyl alcohol is used as a solution, and the mass ratio of the absolute ethyl alcohol to raw materials is 1: 0.6. Spraying the slurry on the middle layer by using compressed high-purity nitrogen at the air displacement of 25-30L/min;
(5) after the coating is prepared, the coating needs to be dried at room temperature for 8 hours, then dried in a 70 ℃ oven for 8 hours, and dried in a 130 ℃ oven for 2 hours;
(6) and (3) placing the coating and the matrix sample in an inert atmosphere for heat treatment, keeping the temperature for 20min after the temperature reaches 1250 ℃, and cooling to obtain the surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material.
The surface of the coating has no obvious defects, the room temperature emissivity is up to 0.85 within the wavelength range of 1.3-2.5 mu m, the binding force between the coating and a substrate is more than or equal to 4MPa, the weight loss rate of the coating is 7.5 percent in 20min and the oxyacetylene ablation rate of the coating is 0.5mm at 1600 ℃ in a high-temperature aerobic environment at 1200 ℃ after the coating is prepared on the surface of a sample.
Example 2
(1) Preparing glass powder: weighing 84% of silicon dioxide and 16% of boron oxide powder by mass, ball-milling and mixing in a mixing tank, then placing in a furnace at 1350 ℃ for heat preservation for 3 hours, taking out and quenching to obtain a glass frit, vibrating and crushing the frit, and grinding the frit into powder for later use;
(2) preparing an inner layer transition coating: weighing 55 mass percent of glass powder, 4 mass percent of silicon hexaboride powder, 48 mass percent of molybdenum disilicide and 15 mass percent of tantalum disilicide, and taking absolute ethyl alcohol as a solution, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 1: 1.4. And carrying out ball milling and mixing treatment for 4h by using a star ball mill at the rotating speed of 180rpm to obtain inner-layer transition layer slurry. Uniformly brushing the slurry on the surface of the carbon-based heat-insulating material to form a coating which penetrates into the matrix to a depth of 1.5-2 mm;
(3) preparing a middle-layer antioxidant coating: weighing 50% of glass powder, 2% of silicon hexaboride, 14% of molybdenum disilicide and 34% of tantalum disilicide powder by mass percent, and carrying out ball-milling mixing treatment for 3h by using a star ball mill at the rotating speed of 200rpm by taking absolute ethyl alcohol as a solution. Spraying the slurry on the transition layer on the surface of the substrate by utilizing compressed high-purity nitrogen at the displacement of 25-30L/min;
(4) preparing a surface high-emissivity coating: weighing 40 mass percent of glass powder, 2 mass percent of silicon hexaboride powder, 20 mass percent of molybdenum disilicide and 36 mass percent of tantalum disilicide, and carrying out ball-milling mixing treatment for 2.5h by using a star-type ball mill at the rotating speed of 200 rpm. Spraying the slurry on the middle layer by using compressed high-purity nitrogen at the air displacement of 25-30L/min;
(5) after the coating is prepared, the coating needs to be dried at room temperature for 8 hours, then dried in a 70 ℃ oven for 8 hours, and dried in a 130 ℃ oven for 2 hours;
(6) and (3) placing the coating and the matrix sample in an inert atmosphere for heat treatment, keeping the temperature for 30min after the temperature reaches 1300 ℃, and cooling to obtain the surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material.
The coating surface has no obvious defects, the temperature emissivity is in the range of 0.87 in the wavelength range of 1.3-2.5 mu m, the binding force between the coating and a substrate is more than or equal to 4MPa, after the coating is prepared on the surface of a sample, the weight loss rate is 11% in 20min and the ablation rate of oxyacetylene is 0.4mm at the temperature of 1600 ℃ in a high-temperature aerobic environment at the temperature of 1300 ℃.
Example 3
(1) Preparing glass powder: weighing 90 mass percent of silicon dioxide and 10 mass percent of boric oxide powder, ball-milling and mixing in a mixing tank, then placing in a furnace at 1400 ℃ for heat preservation for 4 hours, taking out and quenching to obtain glass frit, vibrating and crushing the glass frit, and grinding the glass frit into powder for later use;
(2) preparing an inner layer transition coating: weighing 42 mass percent of glass powder, 1 mass percent of silicon hexaboride powder, 2 mass percent of silicon tetraboride powder, 20 mass percent of molybdenum disilicide and 35 mass percent of tantalum disilicide, and taking absolute ethyl alcohol as a solution, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 1: 1.1. And performing ball milling and mixing treatment for 4 hours by using a star ball mill at the rotating speed of 200rpm to obtain inner-layer transition layer slurry. Uniformly brushing the slurry on the surface of the carbon-based heat-insulating material to form a coating which penetrates into the matrix to a depth of 1.5-2 mm;
(3) preparing a middle-layer antioxidant coating: weighing 62% of glass powder, 1% of silicon hexaboride powder, 2% of silicon tetraboride powder, 10% of molybdenum disilicide and 25% of tantalum disilicide according to mass percent, and carrying out ball-milling and mixing treatment for 4 hours by using absolute ethyl alcohol as a solution and using a star-type ball mill at the rotating speed of 200 rpm. Spraying the slurry on the transition layer on the surface of the substrate by utilizing compressed high-purity nitrogen at the displacement of 25-30L/min;
(4) preparing a surface high-emissivity coating: weighing 34% of glass powder, 2% of silicon hexaboride powder, 1% of silicon tetraboride powder, 13% of molybdenum disilicide and 50% of tantalum disilicide according to mass percent, and carrying out ball-milling mixing treatment for 3 hours at the rotating speed of 200rpm by using a star-type ball mill. Spraying the slurry on the middle layer by using compressed high-purity nitrogen at the air displacement of 25-30L/min;
(5) after the coating is prepared, the coating needs to be dried at room temperature for 8 hours, then dried in a 70 ℃ oven for 8 hours, and dried in a 130 ℃ oven for 2 hours;
(6) and (3) placing the coating and the matrix sample in an inert atmosphere for heat treatment, keeping the temperature for 25min after the temperature reaches 1400 ℃, and cooling to obtain the surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material.
Referring to fig. 1 and fig. 2, the coating surface has no obvious defects, the room temperature emissivity reaches 0.9 in the wavelength range of 1.3-2.5 μm, the binding force between the coating and the substrate is more than or equal to 4MPa, after the coating is prepared on the sample surface, the 20min weight loss rate is 8.5%, and the 1600 ℃ oxyacetylene ablation rate is 0.3mm in the aerobic environment at the high temperature of 1550 ℃.
Example 4
(1) Preparing glass powder: weighing 88 mass percent of silicon dioxide and 12 mass percent of boric oxide powder, ball-milling and mixing in a mixing tank, then placing in a furnace at 1400 ℃ for heat preservation for 4 hours, taking out and quenching to obtain glass frit, vibrating and crushing the glass frit, and grinding the glass frit into powder for later use;
(2) preparing an inner layer transition coating: weighing 42 mass percent of glass powder, 3 mass percent of silicon tetraboride powder, 20 mass percent of molybdenum disilicide and 35 mass percent of tantalum disilicide, and taking absolute ethyl alcohol as a solution, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 1: 1.2. And performing ball milling and mixing treatment for 4 hours by using a star ball mill at the rotating speed of 200rpm to obtain inner-layer transition layer slurry. Uniformly brushing the slurry on the surface of the carbon-based heat-insulating material to form a coating which penetrates into the matrix to a depth of 1.5-2 mm;
(3) preparing a middle-layer antioxidant coating: weighing 60 mass percent of glass powder, 3.5 mass percent of silicon tetraboride, 10 mass percent of molybdenum disilicide and 27.5 mass percent of tantalum disilicide powder, and carrying out ball-milling mixing treatment for 3.5 hours by using a star-type ball mill at the rotating speed of 200rpm by taking absolute ethyl alcohol as a solution. Spraying the slurry on the transition layer on the surface of the substrate by utilizing compressed high-purity nitrogen at the displacement of 25-30L/min;
(4) preparing a surface high-emissivity coating: weighing 32 mass percent of glass powder, 3.5 mass percent of silicon tetraboride powder, 20 mass percent of molybdenum disilicide and 44.5 mass percent of tantalum disilicide, and carrying out ball-milling mixing treatment for 2.5h by using a star-type ball mill at the rotating speed of 200 rpm. Spraying the slurry on the middle layer by using compressed high-purity nitrogen at the air displacement of 25-30L/min;
(5) after the coating is prepared, the coating needs to be dried at room temperature for 8 hours, then dried in a 70 ℃ oven for 8 hours, and dried in a 130 ℃ oven for 2 hours;
(6) and (3) placing the coating and the matrix sample in an inert atmosphere for heat treatment, keeping the temperature for 30min after the temperature reaches 1400 ℃, and cooling to obtain the surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material.
The coating surface has no obvious defects, the temperature emissivity is in the range of 0.89 within the wavelength range of 1.3-2.5 mu m, the binding force between the coating and a substrate is more than or equal to 4MPa, after the coating is prepared on the surface of a sample, the weight loss rate is 10% in 20min and the ablation rate of oxyacetylene at 1600 ℃ is 0.35mm in a high-temperature aerobic environment at 1500 ℃.
Although specific details of the invention are disclosed for purposes of illustration and in order to facilitate an understanding of the contents of the invention and its implementation, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. It is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. A surface oxidation-resistant high-emissivity coating of a porous fibrous carbon-based heat-insulating material comprises an inner-layer transition coating, a middle-layer oxidation-resistant coating and a surface-layer high-emissivity coating; the inner transition coating comprises the following components in percentage by mass: 35-55% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 41-63% of high-emissivity insoluble metal silicide; the middle anti-oxidation coating comprises the following components in percentage by mass: 50-70% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 26-48% of high-emissivity insoluble metal silicide; the surface layer high-emissivity coating comprises the following components in percentage by mass: 30-40% of glass, 2-4% of one or two of silicon hexaboride or silicon tetraboride and 56-68% of high-emissivity insoluble metal silicide.
2. The surface oxidation-resistant high emissivity coating of claim 1, wherein the glass comprises, in weight percent, 75-90% silica and 10-25% boron oxide.
3. The surface oxidation resistant high emissivity coating of claim 1, wherein the high emissivity refractory metal silicide comprises one or both of molybdenum disilicide, tantalum disilicide, and tungsten disilicide.
4. The porous fibrous carbon-based thermal insulation material surface oxidation-resistant high-emissivity coating of claim 1, wherein the inner transition coating penetrates into the base material and has a thickness of 1-2mm, the middle oxidation-resistant coating has a thickness of 100-.
5. The surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material of claim 1, wherein the temperature emissivity of the coating in the wavelength range of 1.3-2.5 μm is greater than 0.85, the bonding force between the coating and the substrate is not lower than 4MPa, the weight loss rate in an aerobic environment at 1300-1550 ℃ is not higher than 12%, and the ablation rate of oxyacetylene at 1600 ℃ is 0.2-0.5 mm.
6. A preparation method of an oxidation-resistant high-emissivity coating on the surface of a porous fibrous carbon-based heat-insulating material comprises the following steps:
(1) preparing glass powder: weighing 75-90% of silicon dioxide and 10-25% of boron oxide powder by mass percent, ball-milling and mixing in a mixing tank, then placing in a 1300-1400 ℃ furnace for heat preservation for 2-4 hours, taking out, cooling in air to obtain glass frit, vibrating and crushing and grinding into powder for later use;
(2) preparing an inner layer transition coating: weighing 35-55% by mass of glass powder, 2-4% by mass of one or two of silicon hexaboride powder and silicon tetraboride and 41-63% by mass of high-emissivity insoluble metal silicide, and performing ball-milling mixing treatment by taking absolute ethyl alcohol as a solution to obtain inner-layer transition layer slurry;
(3) uniformly brushing the slurry uniformly mixed in the step (2) on the surface of the carbon-based heat-insulating material;
(4) preparing a middle-layer antioxidant coating: weighing 50-70% by mass of glass powder, 2-4% by mass of one or two of silicon hexaboride and silicon tetraboride powder, and 26-48% by mass of high-emissivity insoluble metal silicide, and performing ball-milling mixing treatment by taking absolute ethyl alcohol as a solution to obtain middle-layer antioxidation layer slurry;
(5) uniformly spraying the slurry uniformly mixed in the step (4) on the surface of the substrate prepared in the step (3);
(6) preparing a surface high-emissivity coating: weighing 30-40% by mass of glass powder, 2-4% by mass of one or two of silicon hexaboride powder and silicon tetraboride and 56-68% by mass of high-emissivity insoluble metal silicide, and performing ball-milling mixing treatment by taking absolute ethyl alcohol as a solution to obtain surface layer antioxidation layer slurry;
(7) uniformly spraying the slurry uniformly mixed in the step (6) on the surface of the substrate prepared in the step (5);
(8) drying the coating and the substrate, then placing the coating and the substrate in an inert atmosphere for heat treatment, keeping the temperature for 20-30min after the temperature reaches 1250-.
7. The method of claim 6, wherein the high emissivity refractory metal silicide comprises one or both of molybdenum disilicide, tantalum disilicide, and tungsten disilicide.
8. The method for preparing a surface oxidation-resistant high-emissivity coating of a porous fibrous carbon-based heat insulating material according to claim 6, wherein the particle size of the glass powder is in the range of 5 to 10 μm after the molten glass is pulverized in step (1).
9. The preparation method of the surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material according to claim 6, wherein the mass ratio of the absolute ethyl alcohol to the raw materials in the steps (2), (4) and (6) is 1 (0.5-1.5); the ball milling mixing parameters are as follows: ball milling is carried out for 2-4 hours at the rotating speed of 180-200rpm, the ball-material ratio is (2-4):1, and the particle size of the powder after grinding is in the range of 1-3 mu m.
10. The method for preparing the surface oxidation-resistant high-emissivity coating of the porous fibrous carbon-based heat-insulating material according to claim 6, wherein the compressed high-purity nitrogen gas used for spraying in the steps (5) and (7) has an exhaust volume of 25 to 30L/min.
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CN111499414A (en) * 2020-04-10 2020-08-07 中国航天空气动力技术研究院 Light high-strength scouring-resistant ceramic heat-insulation integrated structure and preparation method thereof
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CN113213973A (en) * 2021-05-25 2021-08-06 哈尔滨工业大学 Method for controlling sintering atmosphere of high-emissivity thermal protection coating
CN113307659A (en) * 2021-06-10 2021-08-27 航天特种材料及工艺技术研究所 Preparation method for forming high-emissivity coating on heat insulation tile
CN113307659B (en) * 2021-06-10 2022-04-08 航天特种材料及工艺技术研究所 Preparation method for forming high-emissivity coating on heat insulation tile

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