CN117364052B - High-emissivity rhenium coating and preparation method thereof - Google Patents
High-emissivity rhenium coating and preparation method thereof Download PDFInfo
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- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 96
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 65
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 30
- 239000000460 chlorine Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 238000003754 machining Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 230000008021 deposition Effects 0.000 claims description 61
- 238000005660 chlorination reaction Methods 0.000 claims description 34
- 238000005530 etching Methods 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 abstract description 27
- 238000004663 powder metallurgy Methods 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003749 cleanliness Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000002294 plasma sputter deposition Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000669 biting effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
Abstract
The invention discloses a high-emissivity rhenium coating and a preparation method thereof, and belongs to the technical field of CVD coating preparation. The preparation method of the high-emissivity rhenium coating comprises the following steps: corroding a molybdenum matrix in molten salt; fused salt of NaNO 3 And KNO 3 Mixing the reactants; sequentially chloridizing and depositing in vacuum to obtain a deposited sample; stopping heating, and introducing chlorine gas for 30-60 min at a flow rate of 30-50 ml/min to obtain a rhenium coating molybdenum-based material; finally, the rhenium coating and the molybdenum substrate are separated using a wire-cut electric discharge machining method. According to the invention, the growth orientation of the rhenium coating is regulated and controlled by carrying out molten salt corrosion on the substrate and chlorine corrosion on the deposited sample, the obtained rhenium coating has compact structure, dendritic surface shape, preferred orientation (002) and surface emissivity which can be up to 0.83 and is far higher than that of rhenium prepared by a powder metallurgy method.
Description
Technical Field
The invention belongs to the technical field of CVD coating preparation, and particularly relates to a high-emissivity rhenium coating and a preparation method thereof.
Background
The engine of a spacecraft is a device for generating reactive thrust, and the performance of the engine mainly depends on the working temperature, which is determined by the temperature resistance of the material of an engine thruster (jet pipe). The candidate materials are selected mainly around the melting point, oxidation resistance, thermal stability, strength, thermal expansion coefficient, long-term air tightness, processing performance and the like of the materials. Refractory metals, alloys thereof and ceramic matrix composite materials are important structural materials in the aerospace and cosmic navigation fields because of high melting point and high temperature strength. The materials selected mainly comprise: high melting point metallic materials (niobium, molybdenum, tantalum, platinum group metals, tungsten alloys), ceramic materials, carbon/carbon, iridium/rhenium composites, and the like. Since the 80 s of the 20 th century, the united states aviation and aerospace agency has invested huge capital to start the development plan of the third generation aerospace engine, and the core is to develop structural materials and antioxidation coating materials for ultra-high temperature applications with working temperatures exceeding 1800 ℃. And finally, selecting refractory metal rhenium as a nozzle base material and noble metal iridium as a coating material through large-scale material screening.
Rhenium has high melting point and high hardness, is difficult to prepare and process, and is difficult to be used for preparing and processing rhenium by conventional technologies such as casting, hot forging, turning, welding, processing and the like. Therefore, various technical methods have been developed at home and abroad for the preparation of Re, including powder metallurgy technology, electrodeposition technology, vacuum plasma sputtering technology, chemical vapor deposition technology, and the like. The rhenium material member is prepared by a traditional powder metallurgy method, and is mainly formed by pressing rhenium powder and sintering the rhenium powder at a high temperature, wherein the density of the rhenium material is low. Or adopting cold isostatic pressing blank, further densifying the material by high-temperature hot isostatic pressing to obtain a rhenium spray pipe blank, and then carrying out finish machining to obtain the finished product of the rhenium combustion chamber. The rhenium substrate prepared by powder metallurgy and other methods is easy to deform and lose efficacy when applied at ultra-high temperature; the fused salt electrodeposition prepared rhenium has high speed and low cost, but the deposited material has higher internal stress and can further improve the performance by subsequent heat treatment; rhenium prepared by vacuum plasma sputtering needs to be subjected to multiple heat treatments to improve the microstructure of the material, and the heat treatment process comprises the following steps: and sintering or HIPing after sintering, wherein the density of the final finished product reaches 85-98.7% of the theoretical density. The chemical vapor deposition method is mainly used for preparing rhenium by thermally decomposing and depositing inorganic compounds of rhenium, and the density of the CVD rhenium is close to the theoretical density of the CVD rhenium. However, the quality of the deposited material has higher correlation with technological parameters, the controllability and repeatability of the process are poor, and the fluctuation of technological parameters such as gas flow and the like can lead to the change of material grains and surface morphology, especially the surface morphology has large randomness.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-emissivity rhenium coating and a preparation method thereof. According to the invention, the growth orientation of the rhenium coating is regulated and controlled by carrying out molten salt corrosion on the matrix material and chlorine corrosion on the deposited sample, so that the rhenium coating is compact in structure and has a density which is more than 99.9% of the theoretical density, the surface morphology of the coating material is dendritic, the preferred orientation of the coating material is (002), the surface emissivity can be up to 0.83, and the surface emissivity is far higher than the emissivity (0.28-0.31) of rhenium prepared by a powder metallurgy method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a method for preparing a high emissivity rhenium coating, comprising the steps of:
(1) Polishing the molybdenum substrate, and then corroding in molten salt; fused salt of NaNO 3 And KNO 3 Mixing the reactants;
(2) Pressing raw material rhenium powder into rhenium tablets, and sequentially chloridizing and depositing the rhenium tablets under a vacuum condition to obtain a deposited sample; the chlorination temperature is 800-900 ℃, the deposition temperature is 1100-1300 ℃, and the flow of chlorine is more than 100ml/min during chlorination; deposition time is 10-60 minutes;
(3) Stopping heating after the deposition is finished, and obtaining the rhenium coating molybdenum-based material, wherein the flow rate of the introduced chlorine is 30-50 ml/min and the time is 30-60 min;
(4) The rhenium-coated molybdenum-based material was then separated from the rhenium coating and molybdenum substrate using a wire-cut electric discharge machining process.
As a preferred embodiment of the present invention, naNO 3 And KNO 3 The mass ratio of (2) is 1:1.
as a preferred embodiment of the present invention, the molten salt consists of NaNO 3 And KNO 3 Heating at 300 deg.C for 30 hr.
As a preferred embodiment of the present invention, in the step (1), the etching temperature is 500 to 600℃and the etching time is 50 to 100 hours.
More preferably, the etching temperature is 500℃and the etching time is 100 hours.
As a preferred embodiment of the present invention, in the step (2), the rhenium plate has a diameter of 3-15mm and a thickness of 0.5-5mm.
As a preferred embodiment of the present invention, in the step (2), the degree of vacuum is 10 -2 Torr。
As a preferred embodiment of the present invention, in the step (2), the pressure of the deposition is 0.06-0.07MPa.
As a preferred embodiment of the invention, the purity of Re powder is more than or equal to 99.5%, and the purity of chlorine is more than or equal to 99.5%.
As a preferred embodiment of the invention, the flow rate of the chlorine gas during chlorination is 100-160ml/min.
The invention also claims the high emissivity rhenium coating prepared by the preparation method of the high emissivity rhenium coating.
As a preferred embodiment of the invention, the high emissivity rhenium coating surface is dendritic.
The chemical reaction equation that mainly occurs in the preparation system of the high emissivity rhenium coating:
2Re(s)+5Cl 2 (s)→2ReCl 5 (s)
2ReCl 5 (s)→2Re(s)+5Cl 2 (g)
compared with the prior art, the invention has the beneficial effects that: the invention adopts a CVD method to prepare a rhenium coating on the surface of a molybdenum substrate, wherein the growth of the rhenium coating on the surface of a metal substrate has (002) preferred orientation by carrying out molten salt corrosion on a substrate material, and the shape of the surface of the coating presents dendritic or needle shape; in addition, the chlorine corrosion of the deposited sample can corrode the preferred orientation of a few grains, and the preferred orientation of most (002) is reserved. The prepared rhenium coating has more consistent grain orientation and more excellent performance. The rhenium coating prepared by the invention has compact structure, the density exceeds 99.9% of the theoretical density, the uniformity of the thickness of the coating is easy to control, the dimensional accuracy can reach +/-10 mu m, the emissivity can reach 0.83, and the emissivity is far higher than the emissivity (0.28-0.31) of rhenium prepared by a powder metallurgy method. And the coating quality is convenient to check, the machining waste can be recycled, the cost is low, the size adaptation range is large, and the shape of the matrix material is not particularly limited.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a high-emissivity rhenium coating comprises the following specific steps:
(1) The molybdenum substrate is processed into a cylinder with the diameter of 35mm multiplied by 30mm, the cylinder is ground and polished to improve the cleanliness, and then is subjected to 80-mesh sand polishing pretreatment, and finally is subjected to alcohol wiping and drying. 50wt.% NaNO 3 +50wt.％KNO 3 Placing the mixture in a crucible, uniformly mixing, and heating the mixture in a muffle furnace at 300 ℃ for 30 hours. Placing the substrate in a molten salt crucible, and carrying out molten salt corrosion in a muffle furnace: the etching temperature is 500 ℃ for 100 hours, deionized water is used for cleaning after etching is completed, residual molten salt is removed, and finally drying is carried out.
(2) Pressing the Re powder as a raw material into Re sheets with the diameter of 3mm and the thickness of 5mm to serve as a reaction source of a deposition reaction; and (3) respectively placing the prepared Re sheet and the deposition matrix treated in the step (1) into a chlorination chamber and a deposition chamber, sealing the deposition system, and vacuumizing. Vacuum degree of 10 -2 Torr。
(3) The heating power supply and the induced current of the chlorination chamber are turned on, so that the temperature of the chlorination chamber and the substrate of the deposition chamber reach the set value; the purified chlorine is introduced into the chlorination chamber at a set flow rate. The deposition chamber pressure is adjusted to a predetermined value by controlling the mechanical pump pumping rate. The set temperature of the chlorination chamber is 800 ℃, and the chlorine flow is 100 ml.min -1 The deposition temperature was 1300℃and the deposition time was 10 minutes, the deposition pressure was 0.06MPa.
(4) After the deposition is finished, the heating power supply of the chlorination chamber is turned off, and the flow rate of chlorine is regulated to be 30 ml.min -1 And (3) under the condition that only chlorine is introduced, performing chlorine scouring corrosion on the deposited sample for 30 minutes.
(5) Re and Mo matrix are separated by wire-cut electric discharge machining, and in order to reduce damage to Re, the Re/Mo matrix is separated from the Re/Mo interface by cutting as far as possible, and the residual Mo matrix is removed by mechanical grinding.
The microstructure of the surface of the high-emissivity rhenium coating prepared in the embodiment 1 is in a dendritic morphology, has (002) preferred orientation, the (002) preferred orientation reaches more than 90%, and the emissivity is 0.83 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the uniformity of the thickness of the coating is easy to control, and the dimensional accuracy can reach 10 mu m.
Example 2
A preparation method of a high-emissivity rhenium coating comprises the following specific steps:
(1) The molybdenum substrate is processed into a cylinder with the diameter of 35mm multiplied by 35mm, the cylinder is ground and polished to improve the cleanliness, and then is subjected to polishing pretreatment of 200 meshes, and finally is subjected to alcohol wiping and drying. 50wt.% NaNO 3 +50wt.％KNO 3 Placing the mixture in a crucible, uniformly mixing, and heating the mixture in a muffle furnace at 300 ℃ for 30 hours. Placing the substrate in a molten salt crucible, and carrying out molten salt corrosion in a muffle furnace: the etching temperature is 600 ℃ for 80 hours, deionized water is used for cleaning after etching is completed, residual molten salt is removed, and finally drying is carried out.
(2) Pressing the Re powder as a raw material into Re tablets with the diameter of 15mm and the thickness of 0.5mm to serve as a reaction source of a deposition reaction; and (3) respectively placing the prepared Re sheet and the deposition matrix treated in the step (1) into a chlorination chamber and a deposition chamber, sealing the deposition system, and vacuumizing. Vacuum degree of 10 -2 Torr。
(3) The heating power supply and the induced current of the chlorination chamber are turned on, so that the temperature of the chlorination chamber and the substrate of the deposition chamber reach the set value; the purified chlorine is introduced into the chlorination chamber at a set flow rate. The deposition chamber pressure is adjusted to a predetermined value by controlling the mechanical pump pumping rate. Setting the temperature of the chlorination chamber to 900 ℃, setting the deposition temperature to 1100 ℃ and setting the deposition time to 60 minutes; the chlorine flow is 150 ml.min -1 The deposition pressure was 0.07MPa.
(4) After the deposition is finished, the heating power supply of the chlorination chamber is turned off, and the flow rate of chlorine is regulated to be 50 ml.min -1 In the case where only chlorine is introduced,the deposited sample was subjected to a 60min chlorine washout etch.
(5) Re and Mo matrix are separated by wire-cut electric discharge machining, and in order to reduce damage to Re, the Re/Mo matrix is separated from the Re/Mo interface by cutting as far as possible, and the residual Mo matrix is removed by mechanical grinding.
The microstructure of the surface of the high-emissivity rhenium coating prepared in the embodiment 2 is in a dendritic morphology, has (002) preferred orientation, the (002) preferred orientation reaches more than 90%, the emissivity is 0.81 at 1100 ℃, the rhenium coating is compact in structure, the density is 99.5% of the theoretical density, the uniformity of the thickness of the coating is easy to control, and the dimensional accuracy can reach 10 mu m.
Example 3
The preparation method of the high emissivity rhenium coating in this example is uniquely different from the example in that: in the step (3), the flow rate of chlorine gas is 160ml/min.
As the flow of chlorine increases, the rhenium coating surface of the substrate surface gradually becomes sharp convex from a flat top surface, and the sharp angle height increases. Therefore, the surface of the high emissivity rhenium coating prepared in the comparative example 7 is in an acicular morphology, has over 90 percent of (002) preferred orientation, and has an emissivity of 0.83 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the thickness of the coating is uniform and easy to control, and the dimensional accuracy can reach 10 mu m.
The chlorine flow is increased, so that CVD rhenium deposition is controlled to be changed from quality control to kinetic control, and the growth of the surface with the lowest preferential energy is facilitated under the condition that the chloride is sufficient, the preferential orientation is formed, the preferential orientation is highly concentrated, the sharp surface morphology of the material surface can be improved, and the surface emissivity of the material is improved.
The rhenium coating material has the preferred orientation of more than 90 percent (002), dendritic or needle-shaped morphology, small grain size of less than 10 mu m and higher emissivity at 1100 ℃.
Comparative example 1
A preparation method of a high-emissivity rhenium coating comprises the following specific steps:
(1) The molybdenum substrate is processed into a cylinder with the diameter of 35mm multiplied by 30mm, the cylinder is ground and polished to improve the cleanliness, and then is subjected to 80-mesh sand polishing pretreatment, and finally is subjected to alcohol wiping and drying.
(2) Pressing the Re powder as a raw material into Re sheets with the diameter of 3mm and the thickness of 5mm to serve as a reaction source of a deposition reaction; and (3) respectively placing the prepared Re sheet and the deposition matrix treated in the step (1) into a chlorination chamber and a deposition chamber, sealing the deposition system, and vacuumizing. Vacuum degree of 10 -2 Torr。
(3) The heating power supply and the induced current of the chlorination chamber are turned on, so that the temperature of the chlorination chamber and the substrate of the deposition chamber reach the set value; the purified chlorine is introduced into the chlorination chamber at a set flow rate. The deposition chamber pressure is adjusted to a predetermined value by controlling the mechanical pump pumping rate. The set temperature of the chlorination chamber is 800 ℃, and the chlorine flow is 100 ml.min -1 The deposition temperature was 1300℃and the deposition time was 10 minutes, the deposition pressure was 0.06MPa.
(4) After the deposition, separating Re and Mo matrix by wire-cut electric discharge machining to reduce damage to Re, cutting and separating Re/Mo interface as far as possible, and mechanically grinding to eliminate residual Mo matrix.
The surface of the high emissivity rhenium coating prepared in the comparative example 1 is hexagonal pyramid, has preferred orientations of (002), (103) and (102), and has an emissivity of 0.72 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the thickness of the coating is uniform and easy to control, and the dimensional accuracy can reach 20 mu m.
Comparative example 2
A preparation method of a high-emissivity rhenium coating comprises the following specific steps:
(1) The molybdenum substrate is processed into a cylinder with the diameter of 35mm multiplied by 30mm, the cylinder is ground and polished to improve the cleanliness, and then is subjected to 80-mesh sand polishing pretreatment, and finally is subjected to alcohol wiping and drying.
(2) Pressing the Re powder as a raw material into Re sheets with the diameter of 3mm and the thickness of 5mm to serve as a reaction source of a deposition reaction; and (3) respectively placing the prepared Re sheet and the deposition matrix treated in the step (1) into a chlorination chamber and a deposition chamber, sealing the deposition system, and vacuumizing. Vacuum degree of 10 -2 Torr。
(3) The heating power supply and the induced current of the chlorination chamber are turned on to enable the temperature of the chlorination chamber and the substrate of the deposition chamber to reach the set valueA value; the purified chlorine is introduced into the chlorination chamber at a set flow rate. The deposition chamber pressure is adjusted to a predetermined value by controlling the mechanical pump pumping rate. The set temperature of the chlorination chamber is 800 ℃, and the chlorine flow is 100 ml.min -1 The deposition temperature was 1300℃and the deposition time was 10 minutes, the deposition pressure was 0.06MPa.
(4) After the deposition is finished, the heating power supply of the chlorination chamber is turned off, and the flow rate of chlorine is regulated to be 30 ml.min -1 And (3) under the condition that only chlorine is introduced, performing chlorine scouring corrosion on the deposited sample for 30 minutes.
(5) Re and Mo matrix are separated by wire-cut electric discharge machining, and in order to reduce damage to Re, the Re/Mo matrix is separated from the Re/Mo interface by cutting as far as possible, and the residual Mo matrix is removed by mechanical grinding.
The surface microstructure of the high-emissivity rhenium coating prepared in comparative example 2 is hexagonal pyramid, has preferred orientations of (002), (103) and (102), and has an emissivity of 0.79 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the thickness of the coating is uniform and easy to control, and the dimensional accuracy can reach 15 mu m.
Compared with comparative example 2, after the Mo matrix of example 1 is molten salt etched, a rough structure is formed on the surface, and this concave-convex structure not only forms "anchor" bonding points in the deposition process, increasing the contact area of the rhenium coating and the matrix, but also makes the surface of the metal matrix generate compressive stress, changing the surface activity of the metal matrix, making the growth of the rhenium coating on the surface of the metal matrix have preferred orientation, and the spreading characteristics of the rhenium coating change, forming dendritic surface morphology.
Comparative example 3
A preparation method of a high-emissivity rhenium coating comprises the following specific steps:
(1) The molybdenum substrate is processed into a cylinder with the diameter of 35mm multiplied by 30mm, the cylinder is ground and polished to improve the cleanliness, and then is subjected to 80-mesh sand polishing pretreatment, and finally is subjected to alcohol wiping and drying. 50wt.% NaNO 3 +50wt.％KNO 3 Placing the mixture in a crucible, uniformly mixing, and heating the mixture in a muffle furnace at 300 ℃ for 30 hours. Placing the substrate in a molten salt crucible, and carrying out molten salt corrosion in a muffle furnace: the corrosion temperature is 500 ℃,and (3) after the etching is completed, cleaning the steel plate with deionized water for 100 hours, removing residual molten salt, and finally drying.
(2) Pressing the Re powder as a raw material into Re sheets with the diameter of 3mm and the thickness of 5mm to serve as a reaction source of a deposition reaction; and (3) respectively placing the prepared Re sheet and the deposition matrix treated in the step (1) into a chlorination chamber and a deposition chamber, sealing the deposition system, and vacuumizing. Vacuum degree of 10 -2 Torr。
(3) The heating power supply and the induced current of the chlorination chamber are turned on, so that the temperature of the chlorination chamber and the substrate of the deposition chamber reach the set value; the purified chlorine is introduced into the chlorination chamber at a set flow rate. The deposition chamber pressure is adjusted to a predetermined value by controlling the mechanical pump pumping rate. The set temperature of the chlorination chamber is 800 ℃, and the chlorine flow is 100 ml.min -1 The deposition temperature is 1300 ℃, the deposition time is 10 minutes, and the deposition pressure is 0.06MPa;
(4) Re and Mo matrix are separated by wire-cut electric discharge machining, and in order to reduce damage to Re, the Re/Mo matrix is separated from the Re/Mo interface by cutting as far as possible, and the residual Mo matrix is removed by mechanical grinding.
The surface of the high emissivity rhenium coating prepared in the comparative example 3 is hexagonal pyramid, has preferred orientations of (002), (103) and (102), and has an emissivity of 0.75 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the thickness of the coating is uniform and easy to control, and the dimensional accuracy can reach 12-15 mu m.
Compared with comparative example 3, in example 1, the preferential orientation of (103) and (102) of a few grains can be corroded by continuously introducing chlorine after the deposition is finished, and the preferential orientation of (002) above 90% is reserved.
Comparative example 4
The only difference between the preparation method of the high emissivity rhenium coating described in this comparative example and example 1 is that: in the step (1), the etching temperature is 400 ℃ and the etching time is 40 hours.
The corrosion temperature is insufficient, the surface roughness of the molybdenum substrate is small due to short time, the biting effect of the rhenium coating and the surface of the metal substrate is not obvious, the compressive stress generated by the surface corrosion of the metal substrate is easy to eliminate, and the preferential orientation surface is less exposed. The preferred orientation growth tissue of the rhenium coating prepared in the comparative example 4 is not highly concentrated, the hexagonal pyramid has wide bottom surface and short tip, has preferred orientations of (002), (102) and (103), and has an emissivity of 0.78 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the thickness of the coating is uniform and easy to control, and the dimensional accuracy can reach 12-15 mu m.
Comparative example 5
The preparation method of the high emissivity rhenium coating in this comparative example is uniquely different from the examples in that: in the step (1), the etching temperature is 700 ℃ and the etching time is 110 hours.
The corrosion temperature is too high and the time is too long, so that the prepared coating is uneven in thickness, small in adhesive force, and bubbles are easy to be trapped in narrow and deeper trough positions, so that bubbling of the coating is caused. The surface of the high emissivity rhenium coating prepared in the comparative example 5 is in a stepped hexagonal pyramid shape, has preferred orientations of (002), (102) and (103), and has an emissivity of 0.74 at 1100 ℃; the rhenium coating has basically compact structure, the density is 98.2% of the theoretical density, the thickness measurement of the coating has certain deviation, and the dimensional accuracy can reach 8-15 mu m.
Comparative example 6
The only difference between the preparation method of the high emissivity rhenium coating described in this comparative example and example 1 is that: in step (3), the deposition temperature was 1400 ℃.
As the deposition temperature increases, the morphology of the rhenium coating growth particles on the surface of the substrate of comparative example 6 is changed from wedge shape to wide-base hexagonal pyramid morphology, while the preferred orientation of (002) is maintained, the grains are coarse, the surface area is reduced, and the emissivity is obviously reduced to 0.72 at 1100 ℃; the rhenium coating has compact structure, the density is 99.9% of the theoretical density, the thickness of the coating is uniform and easy to control, and the dimensional accuracy can reach 22.7 mu m.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A method for preparing a high emissivity rhenium coating, comprising the steps of:
(1) Polishing the molybdenum substrate, and then corroding in molten salt; fused salt of NaNO 3 And KNO 3 Mixing the reactants; the corrosion temperature is 500-600 ℃ and the corrosion time is 50-100h;
(2) Pressing raw material rhenium powder into rhenium tablets, and sequentially chloridizing and depositing the rhenium tablets under a vacuum condition to obtain a deposited sample; the chlorination temperature is 800-900 ℃, the deposition temperature is 1100-1300 ℃, and the flow of chlorine is more than 100ml/min during chlorination; deposition time is 10-60 minutes;
(3) Stopping heating after the deposition is finished, and introducing chlorine at a flow rate of 30-50 ml/min for 30-60 min to obtain a rhenium coating molybdenum-based material;
(4) The rhenium-coated molybdenum-based material was then separated from the rhenium coating and molybdenum substrate using a wire-cut electric discharge machining process.
2. The method of preparing a high emissivity rhenium coating of claim 1, wherein said NaNO 3 And KNO 3 The mass ratio of (2) is 1:1.
3. the method for preparing a high emissivity rhenium coating of claim 1, wherein said molten salt is formed from NaNO 3 And KNO 3 Heating at 300 deg.C for 30 hr.
4. The method of preparing a high emissivity rhenium coating of claim 1, wherein the etching is performed at a temperature of 500 ℃ for a period of 100 hours.
5. The method for preparing a high emissivity rhenium coating of claim 1, wherein in step (2), the vacuum level is 10 -2 Torr。
6. The method for preparing a high emissivity rhenium coating of claim 1, wherein in step (2), the deposition pressure is in the range of 0.06MPa to 0.07MPa.
7. The method for preparing a high emissivity rhenium coating of claim 1, wherein the chlorine gas is at a flow rate of 100-160ml/min during the chlorination.
8. A high emissivity rhenium coating prepared by the method of any one of claims 1-7.
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| US11532474B2 (en) * | 2019-08-12 | 2022-12-20 | Applied Materials, Inc. | Deposition of rhenium-containing thin films |
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