CN116334525A - High-emissivity coating and preparation method thereof - Google Patents
High-emissivity coating and preparation method thereof Download PDFInfo
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- CN116334525A CN116334525A CN202310068217.5A CN202310068217A CN116334525A CN 116334525 A CN116334525 A CN 116334525A CN 202310068217 A CN202310068217 A CN 202310068217A CN 116334525 A CN116334525 A CN 116334525A
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- 238000000576 coating method Methods 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000000919 ceramic Substances 0.000 claims abstract description 27
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical group [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001120 nichrome Inorganic materials 0.000 claims abstract description 21
- 230000007704 transition Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 19
- 238000007750 plasma spraying Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010290 vacuum plasma spraying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 43
- 238000012360 testing method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000009863 impact test Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- C23C4/08—Metallic material containing only metal elements
-
- 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
Abstract
The invention relates to a high-emissivity coating and a preparation method thereof. The high emissivity coating comprises: the metal transition layer and the TiC ceramic layer are sequentially formed on the surface of the base material; the metal transition layer is a NiCr alloy layer or a W metal layer, preferably a W metal layer.
Description
Technical Field
The invention relates to a high-emissivity coating and a preparation method thereof, and belongs to the technical field of plasma spraying coatings.
Background
The high emissivity coating is a thermal protection material, can enhance the radiation and heat dissipation characteristics of the surface of the workpiece, and has the purposes of regulating and controlling the temperature of the workpiece and improving the service life and reliability of the workpiece. High-speed aircrafts, aerospace thrusters, industrial kilns and other national defense, aviation, aerospace and metallurgical field equipment have great demands for high-emissivity coatings. During the service process of the workpiece, the surface can generate very high heat and rapidly heat up. The coating is required to have a high emissivity at high temperatures and to be able to scatter rapidly. And the workpiece can experience multiple thermal shocks, and the coating is required to have better high-temperature and low-temperature impact resistance. The research and development of the high-emissivity coating has important scientific significance and application value. In the aspect of the preparation technology of the coating, the plasma spraying technology has little requirement on the matrix, can spray the inner wall of a special-shaped piece or part, has wide application range of spraying materials, controllable thickness of the coating and wide range (a few micrometers to a few millimeters), has good process stability, high bonding strength of the coating and the matrix and reliable quality of the coating.
Disclosure of Invention
The invention aims to provide a high-emissivity coating which has higher emissivity, good high-low temperature impact resistance and better combination with a matrix. The heat accumulated on the surface of the workpiece can be radiated in a radiation mode, so that the reliable service life of the workpiece is effectively prolonged.
The invention also aims to provide a preparation method of the high-emissivity coating, which adopts a plasma spraying technology to prepare the NiCr or W metal layer and the TiC ceramic layer which have good melting effect and high bonding strength with the matrix.
In one aspect, the present invention provides a high emissivity coating comprising: the metal transition layer and the TiC ceramic layer are sequentially formed on the surface of the base material; the metal transition layer is a NiCr alloy layer or a W metal layer, preferably a W metal layer.
In the invention, the TiC ceramic layer has higher room temperature and high temperature emissivity, can endow the part with good surface radiation heat dissipation performance, and the NiCr or W metal layer is used as a bonding layer between the matrix and the TiC ceramic layer, so that the physical compatibility of the matrix and the ceramic surface layer can be improved. The bonding performance between the NiCr or W metal layer and the TiC ceramic layer and between the NiCr or W metal layer and the matrix is good. Preferably, the NiCr coating with the Cr content of 19-21 wt.% has good binding property and toughness, and can improve the thermal shock resistance of the coating system. W has a high melting point and extremely low high temperature saturated vapor pressure, which reduces or even avoids the risk of coating failure due to rapid dissipation of the transition layer in a high temperature high vacuum application environment. And at high temperature, W has better plasticity (the ductile-brittle transition temperature of pure W is about 550 ℃), and excessive peeling stress caused by thermal mismatch is avoided, so that TiC can be continuously attached to the surface without falling off.
Preferably, the TiC ceramic layer has a TiC phase as the main phase and contains no more than 3wt% of TiO x Phase, wherein x is more than or equal to 1 and less than or equal to 2.
Preferably, the Cr content in the NiCr alloy layer is 19wt.% to 21wt.%, and the balance is Ni.
Preferably, the thickness of the metal transition layer is 10-80 μm. The transition layer has the function of tightly combining the base material and the TiC layer, so that the thermal shock resistance is improved.
Preferably, the TiC ceramic layer has a thickness of 40-120 μm.
Preferably, the total thickness of the metal transition layer and the TiC ceramic layer is 50-200 mu m.
Preferably, the matrix comprises one of a metal matrix, a graphite matrix and a ceramic matrix. The type of substrate is not limited and includes, but is not limited to, one of superalloy, stainless steel, soft iron, tungsten-rhenium alloy.
Preferably, the high-temperature emissivity of the high-emissivity coating is more than or equal to 0.8 (normal emissivity at 500 ℃); the bonding strength of the high-emissivity coating and the matrix is more than or equal to 40MPa.
On the other hand, the invention provides a preparation method of the high-emissivity coating, wherein one of NiCr or W powder is used as a spraying raw material, and a transition metal layer is prepared on the surface of a substrate by adopting a plasma spraying method;
and preparing a TiC ceramic layer on the surface of the transition metal layer by using TiC powder as a spraying raw material and adopting a plasma spraying method to obtain the high-emissivity coating. The preparation method of the invention can obtain the NiCr or W metal layer and TiC ceramic layer which have good melting effect and are well combined with the matrix.
Preferably, the composition of the NiCr powder includes: cr:19wt.% to 21wt.%, balance Ni; the W powder comprises the following components: w is more than or equal to 99wt.%; the TiC powder comprises the following components: tiC is more than or equal to 97wt.%.
Preferably, the median particle diameter of the NiCr powder is 30-75 mu m; the median particle diameter of the W powder is 30-60 mu m; the median particle diameter of the TiC powder is 10-55 mu m.
Preferably, the plasma spraying method comprises the following steps: atmospheric plasma spraying and vacuum plasma spraying; atmospheric plasma spraying is preferred.
Preferably, the process parameters of the atmospheric plasma spraying include: argon flow 43-53 slpm, hydrogen flow 7-10 slpm, current 600-700A, powder feeding carrier gas flow 3-5 slpm, spraying distance 115-135 mm.
The beneficial effects are that:
in the invention, the high-temperature emissivity of the high-emissivity coating can reach more than 0.8 (normal emissivity at 500 ℃), and the bonding strength with a metal matrix can reach more than 40MPa. The coating has excellent high and low temperature impact resistance, and remains intact after 200 times of cold and hot alternation at the temperature of 200 ℃ and liquid nitrogen.
Drawings
FIG. 1 is an XRD pattern photograph of TiC ceramic powder and a spray-applied coating sample of example 1;
FIG. 2 is a photograph of a sample of the spray-applied coating of example 1;
FIG. 3 is a photograph of a sample of the spray-applied coating of example 2;
FIG. 4 is a photograph of a sample of the spray-applied coating of example 4;
FIG. 5 is a photograph of a sample of the spray-applied coating of example 5.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the high emissivity coating is a bilayer structure comprising a metallic transition layer and (e.g., a NiCr or W metal layer) and a TiC ceramic layer formed on the surface of the substrate.
In an alternative embodiment, the TiC ceramic layer is predominantly TiC phase, allowing for a small content of TiO x And (3) phase (C).
In one embodiment of the invention, a W metal layer and a TiC ceramic layer are sequentially prepared on the surface of a metal substrate by using an atmospheric plasma spraying technology. The following illustrates an exemplary method of preparing a high emissivity coating.
Deposition of NiCr or W powder. Specifically, a plasma spraying technology is adopted to deposit NiCr powder or W powder on the surface of a substrate. And cleaning and sand blasting the substrate before spraying.
And (3) deposition of TiC ceramic powder. Specifically, tiC powder is deposited on the surface of the metal layer by adopting a plasma spraying technology.
In the invention, according to the GJB 2502.3-2006 spacecraft thermal control coating test method part 3: emissivity test the high temperature emissivity of the obtained high emissivity coating can reach more than 0.8 (normal emissivity at 500 ℃).
In the invention, the bonding strength between the high emissivity coating and the metal matrix can reach more than 40MPa according to the test of GB/T8642-2002 thermal spraying-tensile bonding strength determination.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) The sample matrix was stainless steel (square test piece). Pretreatment of the surface of a metal substrate to be sprayed: sand blasting, ultrasonic cleaning and compressed air drying;
(2) And (3) taking W powder as a raw material, and adopting an atmospheric plasma spraying process to deposit a W coating on the surface of the metal matrix. The impurity content of the W powder is less than or equal to 1 wt%. The spraying parameters are as follows: argon flow 46+ -3 slpm, hydrogen flow 8.5+ -1.5 slpm, current 650+ -10A, powder feeding carrier gas flow 4+ -1 slpm, spraying distance 120+ -5 mm.
(3) TiC ceramic powder is used as a raw material, and an atmospheric plasma spraying process is adopted to deposit a TiC ceramic coating on the surface of the W metal layer. The impurity content of the ceramic powder is less than or equal to 3 wt%. The spraying parameters are as follows: argon flow 50+/-3 slpm, hydrogen flow 8.5+/-1.5 slpm, current 650+/-10A, powder feeding carrier gas flow 4+/-1 slpm and spraying distance 130+/-5 mm.
FIG. 1 is an XRD pattern of TiC ceramic powder and as-sprayed coating samples. Fig. 2 is a photograph of a sample of the as-sprayed coating. The thickness of the W metal layer is about 20 mu m, and the thickness of the TiC coating layer is about 60 mu m; the total thickness of the W metal layer and TiC coating layer was 100.+ -.50. Mu.m. The sample was subjected to emissivity test (wavelength 4 to 25 μm) at room temperature, and the test value was 0.70.
Example 2
The difference from example 1 is that: the substrate shapes and sizes were different (round test pieces), and the metal layer was a NiCr alloy layer (thickness: about 20 μm) prepared in the same manner as in example 1. Fig. 3 is a photograph thereof. The coatings were tested for high temperature emissivity. The sample was heated to 500℃and the test wavelength was 4-25 μm with a normal emissivity of 0.88.
Example 3
The difference from example 1 is that: the shape and size of the matrix were different (cylindrical samples), and the preparation method was the same as in example 1. The test pieces were subjected to a bond strength test with a test value of 47.7.+ -. 4.8MPa.
Example 4
The difference from example 3 is that: the base materials are different, and the base is high-temperature alloy (GH 3128). The preparation method is the same as in example 3. Fig. 4 is a photograph thereof. The sample is subjected to liquid nitrogen high-low temperature impact test at the temperature of 200 ℃ and the coating is intact after 10 times. After impact for 10 times at high and low temperature of liquid nitrogen-200 ℃, the bonding strength test value is 46.9+/-3.9 MPa. Compared with the example 3, the coating is sprayed with a W and TiC double-layer structure coating on the surfaces of the stainless steel substrate and the high-temperature alloy substrate after being subjected to cold and hot alternation of liquid nitrogen to 200 ℃ for 10 times, the measured value of the bonding strength is not obviously different, and the coating and the substrate still have higher bonding force.
Example 5
The difference from example 1 is that: the base materials and the shapes and sizes are different (circular and circular ring samples), and the base is tungsten-rhenium alloy. Fig. 5 is a photograph thereof. The sample is subjected to liquid nitrogen high-low temperature impact test at the temperature of 200 ℃, and the coating is good after 200 times.
Comparative example 1
The difference from example 4 is that: without the W metal layer, only the TiC coating had a thickness of about 60 μm. And (3) performing liquid nitrogen-200 ℃ high-low temperature impact test on the sample, and removing the coating after 5 times.
Claims (10)
1. A high emissivity coating comprising: the metal transition layer and the TiC ceramic layer are sequentially formed on the surface of the base material; the metal transition layer is a NiCr alloy layer or a W metal layer, preferably a W metal layer.
2. The high emissivity coating of claim 1 wherein said TiC ceramic layer has a major TiC phase comprising no more than 3wt% TiO x A phase, wherein x is more than or equal to 1 and less than or equal to 2; the content of Cr in the NiCr alloy layer is 19-21 wt.%, and the balance is Ni.
3. The high emissivity coating of claim 1, wherein said metal transition layer has a thickness of 10 to 80 μm and said TiC ceramic layer has a thickness of 40 to 120 μm;
preferably, the total thickness of the metal transition layer and TiC ceramic layer is 50-200 μm.
4. The high emissivity coating of claim 1 wherein said substrate comprises one of a metal substrate, a graphite substrate, and a ceramic substrate.
5. The high emissivity coating of any one of claims 1 to 4, wherein the high temperature emissivity of the high emissivity coating is ≡0.8 (500 ℃ normal emissivity); the bonding strength of the high-emissivity coating and the matrix is more than or equal to 40MPa.
6. A method for producing a high emissivity coating according to any one of claims 1 to 5, characterized in that a transition metal layer is produced on the surface of a substrate by a plasma spraying method using one of NiCr or W powder as a spray material;
and preparing a TiC ceramic layer on the surface of the transition metal layer by using TiC powder as a spraying raw material and adopting a plasma spraying method to obtain the high-emissivity coating.
7. The method according to claim 6, wherein the composition of the NiCr powder comprises: cr:19wt.% to 21wt.%, balance Ni; the W powder comprises the following components: w is more than or equal to 99wt.%; the TiC powder comprises the following components: tiC is more than or equal to 97wt.%.
8. The method according to claim 6, wherein the NiCr powder has a median particle diameter of 30 to 75 μm; the median particle diameter of the W powder is 30-60 mu m; the median particle diameter of the TiC powder is 10-55 mu m.
9. The method of any one of claims 6-8, wherein the plasma spraying method comprises: atmospheric plasma spraying and vacuum plasma spraying; atmospheric plasma spraying is preferred.
10. The method of claim 9, wherein the process parameters of the atmospheric plasma spray include: argon flow 43-53 slpm, hydrogen flow 7-10 slpm, current 600-700A, powder feeding carrier gas flow 3-5 slpm, spraying distance 115-135 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310068217.5A CN116334525A (en) | 2023-02-06 | 2023-02-06 | High-emissivity coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310068217.5A CN116334525A (en) | 2023-02-06 | 2023-02-06 | High-emissivity coating and preparation method thereof |
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| CN116334525A true CN116334525A (en) | 2023-06-27 |
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| CN202310068217.5A Pending CN116334525A (en) | 2023-02-06 | 2023-02-06 | High-emissivity coating and preparation method thereof |
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| CN (1) | CN116334525A (en) |
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2023
- 2023-02-06 CN CN202310068217.5A patent/CN116334525A/en active Pending
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