CN110863167A - Niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and preparation method thereof - Google Patents

Niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and preparation method thereof Download PDF

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CN110863167A
CN110863167A CN201911239360.6A CN201911239360A CN110863167A CN 110863167 A CN110863167 A CN 110863167A CN 201911239360 A CN201911239360 A CN 201911239360A CN 110863167 A CN110863167 A CN 110863167A
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niobium
tungsten alloy
resistant coating
oxidation
transition layer
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陈实
吕树元
徐健博
邱新潮
张博文
钟复港
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • 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
    • C23C4/18—After-treatment

Abstract

The invention discloses a niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and a preparation method thereof, and belongs to the field of ultrahigh-temperature thermal protection. The method comprises the following steps: the surface of the niobium-tungsten alloy matrix is subjected to laser roughening treatment; and the niobium-tungsten alloy anti-oxidation coating is attached to the surface of the niobium-tungsten alloy matrix roughened by the laser. According to the invention, the surface of the niobium-tungsten alloy is subjected to laser roughening treatment, longitudinal stripes are etched to increase the roughness of the surface of the matrix, and then the transition layer and the oxygen barrier layer are prepared on the surface, so that the niobium-tungsten alloy is more firmly attached to the matrix. The transition layer and the oxygen barrier layer are densified through an isostatic pressing process, the thickness of the oxidation-resistant coating can be directly reduced by 20-40%, the densification degree of the oxidation-resistant coating is greatly increased, the heat treatment is combined, the annealing process eliminates the residual stress in the oxidation-resistant coating to a certain degree, and the sintering process increases the grain size in the oxidation-resistant coating, so that the oxidation-resistant ablation capacity, the stability and the thermal shock resistance are enhanced.

Description

Niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and preparation method thereof
Technical Field
The invention belongs to the field of ultra-high temperature thermal protection, and particularly relates to a niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure and a preparation method thereof.
Background
The spacecraft engine is mainly applied to carrier rockets, satellites and airships, is a highly complex and precise thermal machine, provides flying power for the spacecraft, and can directly influence the performance, reliability and economy of the spacecraft. In order to ensure that the engine part of the spacecraft has a certain service life, the materials are required to simultaneously meet the requirements of sufficient high-low temperature mechanical properties, good hot corrosion performance, high-temperature oxidation resistance and thermal shock resistance. With the rapid development of the space detection technology, the thrust-weight ratio of the engine is higher and higher, and the working temperature is also obviously improved, so that the development of the ultra-high temperature alloy material with excellent high temperature mechanical property, thermal strength and high temperature oxidation resistance is imperative.
The spacecraft is mainly used for attitude control, orbit control, butt joint and intersection of the spacecraft and the like in space and is a low-thrust liquid rocket engine. The method is characterized in that the pulse operation is started for many times in a space environment, the thrust is small and is generally 0.001-4500N, the minimum pulse width is millisecond, and the total working time (the sum of the working time and the clearance time) can reach 5-10 years, so that higher requirements on the thermal shock resistance of the material are provided. With the development of spacecrafts, a light-weight and high-performance low-thrust two-component liquid rocket engine is needed to increase the effective load of a satellite; the device is suitable for the requirements of continuous conversion from a kinetic energy interceptor to quick response, light weight, low cost and safety, a deep space probe propulsion system needs high performance, long service life, repeated starting and no plume pollution, and higher requirements are provided for the structural quality and performance of a low-thrust attitude/rail-controlled engine. The performance of the propulsion system is improved by new materials and new processes, the effective load can be increased, the service life of the spacecraft is prolonged, and the long-term reliable work of the engine is ensured.
Niobium (Nb) belongs to VB group refractory metal, has a melting point of 2648 ℃, has a bcc structure and a thermal expansion coefficient of 7.2 x 10-6K-1The density is similar to that of steel and is 8.56g cm-3The strength can be kept to 1649 ℃ and certain mechanical deformation can be borne. Pure niobium has high solid solubility for many strengthening elements such as W, Mo, Zr, etc. Based on the excellent physical and chemical properties of the niobium and the alloy thereof, the niobium and the alloy thereof can be used as the main selection of the ultrahigh-temperature alloy material of the rail attitude control liquid engine, but the niobium and the alloy thereof have the phenomena of pulverization, plague and oxidation at 600-800 ℃, the oxide layer can be cracked by the internal stress generated on the interface of the oxide and the metal along with the thickening of the oxide layer, and then the catastrophic oxidation occurs, thereby seriously limiting the application of the niobium and the alloy thereof in the high-temperature aerobic environment. Meanwhile, the research of the niobium alloy is mainly focused on alloying modification and coating, the alloying improves the oxidation resistance of the alloy to a certain extent, but can seriously affect the high-temperature mechanical property of the alloy, and the surface coating can not affect the good high-temperature mechanical property of the niobium alloy and effectively protect the base material to work in a high-temperature aerobic environment. Therefore, the high-temperature oxidation resistance of the surface coating directly determines the working temperature of the niobium-tungsten alloy for the aerospace aircraft engine, and indirectly influences the quality and the performance of the aerospace aircraft engine, so that the coating matched with the niobium-based alloy is required to be used for improving the high-temperature oxidation resistance of the niobium-tungsten alloy.
Disclosure of Invention
Aiming at the problem of insufficient thermal shock resistance of an oxygen barrier layer in the prior art, the invention provides a niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and a preparation method thereof, and aims to coarsen the surface of the niobium-tungsten alloy by laser, etch a groove to form certain roughness, prepare a transition layer and an oxygen barrier layer outside, and perform isostatic pressing and heat treatment on a sample to enhance the compactness of the coating, reduce microcracks, reduce porosity and release thermal stress, and meanwhile, the thermal shock resistance of the coating is remarkably enhanced.
To achieve the above object, according to a first aspect of the present invention, there is provided a niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure, comprising:
the surface of the niobium-tungsten alloy matrix is subjected to laser roughening treatment;
and the niobium-tungsten alloy anti-oxidation coating is attached to the surface of the niobium-tungsten alloy matrix roughened by the laser.
Preferably, the laser roughening treatment is performed to obtain transverse/longitudinal stripes with a depth of 10-50 μm and an interval of 50-200 μm.
Preferably, the niobium tungsten alloy oxidation resistant coating comprises: the niobium-tungsten alloy oxidation-resistant coating comprises a transition layer and an oxygen barrier layer, wherein the transition layer is positioned on the surface of the niobium-tungsten alloy substrate, the oxygen barrier layer is positioned on the surface of the transition layer, and the niobium-tungsten alloy oxidation-resistant coating is subjected to densification treatment.
Preferably, the thermal expansion coefficient of the material of the transition layer is between the materials selected for the niobium-tungsten alloy and the oxygen barrier layer.
Preferably, the transition layer is a thin film layer with the thickness of 10-60 mu m.
Preferably, the transition layer is one of silicon carbide, molybdenum silicide, tungsten carbide, tantalum, niobium silicide or magnesium oxide.
Preferably, the oxygen barrier layer is a composite coating having a thickness greater than 60 μm and less than 200 μm.
Preferably, the oxygen barrier layer is at least one of titanium oxide, haar oxide, magnesium oxide, hafnium carbide, tantalum carbide, silicon carbide and zirconium boride.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for preparing the niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure, the method comprising the following steps:
s1, carving stripes on the niobium-tungsten alloy through a laser;
s2, preparing a transition layer on the surface of the niobium-tungsten alloy substrate;
s3, preparing an oxygen barrier layer on the surface of the transition layer;
and S4, performing densification treatment on the prepared niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating.
Preferably, the transition layer and the oxygen barrier layer are densified by an isostatic pressing and annealing process.
Generally, by the above technical solution conceived by the present invention, the following beneficial effects can be obtained:
(1) according to the invention, the surface of the niobium-tungsten alloy is subjected to laser roughening treatment, transverse/longitudinal stripes are etched, the roughness of the surface of the matrix is increased, and then the transition layer and the oxygen barrier layer are prepared on the surface, so that the niobium-tungsten alloy is more firmly attached to the matrix.
(2) According to the invention, the transition layer and the oxygen barrier layer are densified through an isostatic pressing process, the thickness of the oxidation-resistant coating can be directly reduced by 20-40%, the densification degree of the oxidation-resistant coating is greatly increased, the residual stress in the oxidation-resistant coating is released to a certain extent through the combination of a heat treatment and an annealing process, and the grain size in the oxidation-resistant coating is increased through a sintering process, so that the oxidation-resistant ablation capacity and the stability are enhanced.
(3) According to the invention, the stability and the thermal shock resistance of the coating of the oxygen barrier layer prepared by coarsening the matrix by laser are obviously enhanced.
(4) The transition layer prepared by the method is directly positioned on the surface of the niobium-tungsten alloy, the thickness of the transition layer is 10-60 mu m, the adhesion between the niobium-tungsten alloy matrix and the oxidation resistant layer can be improved by the transition layer, and meanwhile, the mismatch of thermal expansion coefficients and certain oxidation resistance can be relieved.
Drawings
FIG. 1 is a schematic diagram of a longitudinal stripe structure etched on a niobium-tungsten alloy substrate by using an ultraviolet nanosecond laser according to an embodiment of the invention;
FIG. 2 is a schematic microscopic view of the niobium-tungsten alloy ultra-high temperature oxidation resistant coating based on laser roughening, which is provided in example 1 of the present invention, and is subjected to thermal shock at 1500 ℃ for 100 times;
FIG. 3 is a microscopic view of the niobium-tungsten alloy ultra-high temperature oxidation resistant coating without laser roughening, provided by example 2 of the invention, after being thermally shocked at 1500 ℃ for 100 times.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the present invention provides a niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure, which comprises:
the surface of the niobium-tungsten alloy matrix is subjected to laser roughening treatment;
and the niobium-tungsten alloy anti-oxidation coating is attached to the surface of the niobium-tungsten alloy matrix roughened by the laser.
The surface of the matrix is coarsened and modified by laser to enhance the thermal shock resistance. Preferably, the laser roughening treatment has stripe depth of 10-50 μm and interval of 50-200 μm, and may be transverse stripe or longitudinal stripe.
Preferably, the niobium tungsten alloy oxidation resistant coating comprises: the transition layer is positioned on the surface of the niobium-tungsten alloy substrate, and the oxygen barrier layer is positioned on the surface of the transition layer. The niobium-tungsten alloy oxidation resistant coating is subjected to densification treatment. Therefore, the thickness of the oxidation-resistant coating can be directly reduced by 20-40%, and the densification degree of the oxidation-resistant coating is greatly increased.
Preferably, the thermal expansion coefficient of the material of the transition layer is between the materials of the niobium-tungsten alloy and the oxygen barrier layer, so that the difference between the thermal expansion coefficients can be relieved.
The material selected for the transition layer in the preferable coating structure of the niobium-tungsten alloy anti-oxidation coating does not react with the niobium-tungsten alloy substrate at the temperature of more than 2000 ℃, and the absolute value of the difference of the thermal expansion coefficients of any two of the niobium-tungsten alloy substrate, the transition layer and the oxygen barrier layer is not more than 3 x 10-6K-1. Generally, the thermal expansion coefficient of the niobium-tungsten alloy matrix is the minimum, and the thermal expansion coefficients are increased from inside to outside in sequence.
The transition layer has the functions of relieving the mismatching of the thermal expansion coefficients, increasing the adhesive force of the oxygen barrier layer and having certain oxidation resistance. Preferably, the transition layer is made of a refractory material which is tightly combined with the matrix and has a high melting point, excellent high-temperature mechanical properties, certain oxidation resistance and the like. Specifically, it is one of silicon carbide, molybdenum silicide, tungsten carbide, tantalum, niobium silicide, or magnesium oxide. The transition layer is preferably a thin film layer with the thickness of 10-60 mu m through simulation calculation. The thermal stress in the thickness range is small, the performance of the coating is influenced by the thermal stress, and the coating can crack and even peel off due to the thermal stress, so that the oxidation resistance is greatly reduced.
The oxygen barrier layer has a high melting point, is uniform and compact, has a certain self-healing capacity at a high temperature, and can weaken cracks and have a certain oxygen diffusivity and oxidation resistance. Preferably, the oxygen barrier layer is preferably made of refractory metal oxide, ultrahigh temperature ceramic material and the like, has ultrahigh melting point, high hardness, high stability and good high temperature strength, and can play a role in resisting oxygen ablation at the temperature of more than 2000 ℃. Specifically, the material is at least one of titanium oxide, haar oxide, magnesium oxide, hafnium carbide, tantalum carbide, silicon carbide and zirconium boride. The following results are obtained through simulation calculation: the total thickness of the oxygen barrier layer is greater than 60 μm and less than 200 μm. The thermal stress is small in this thickness range, and the adhesion force is preferable in this thickness range from the viewpoint of the process.
The invention provides a preparation method of the niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure, which comprises the following steps:
and S1, engraving stripes on the niobium-tungsten alloy through a laser.
In the embodiment, an ultraviolet nanosecond laser is selected, the laser frequency is 30-60 kHz, the power is 1-9 w, and the higher the power is, the higher the energy is, the fewer the ablation times are. In the embodiment, the etching times are 10-50 times, the etching rate is 50-200 mm/s, the slower the etching rate is, the higher the energy at the position is, and the etching depth is increased.
The niobium-tungsten alloy is firstly put into 98 percent concentrated sulfuric acid for ultrasonic cleaning for 30min to remove oxides generated on the surface. And then the substrate is placed in a saturated sodium hydroxide aqueous solution for ultrasonic cleaning for 30min to further remove the oxide generated on the surface. And then the glass is placed in deionized water for ultrasonic cleaning for 15min so as to clean and remove the particles attached to the surface. Finally, placing the mixture in absolute ethyl alcohol for ultrasonic cleaning for 15min to further remove surface particles, and simultaneously facilitating blow drying.
S2, preparing a transition layer on the surface of the niobium-tungsten alloy substrate.
Preferably, the transition layer is prepared on the surface of the niobium-tungsten alloy matrix by a magnetron sputtering method, a thermal spraying method, a chemical vapor deposition method or an embedding method.
And S3, preparing an oxygen barrier layer on the surface of the transition layer.
Preferably, the oxygen barrier layer is prepared on the surface of the transition layer by a chemical vapor deposition method, a thermal spray method or a sol-gel method.
And S4, performing densification treatment on the prepared niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating.
Preferably, the transition layer and the oxygen barrier layer are densified by an isostatic pressing and annealing process. The pressure maintaining pressure of the isostatic pressing process is 50-200 Mpa, generally 100Mpa is used, the pressure can make the coating compact, and meanwhile, the substrate and the material cannot be damaged. The pressure maintaining time is 10-30 min, the pressure can be flexibly set, the longer the pressure maintaining time is, the more compact the coating is, but the compactness can not be improved to a certain degree.
Since the temperature below 700 ℃ can not eliminate some defects and residual stress, and the grain size is smaller, the coating compactness is also poor. And the equipment cannot reach a temperature higher than 1700 c, the maximum temperature is set to 1700 c. The annealing process is to carry out heat preservation treatment for 1 hour at 700-1700 ℃ under the protection atmosphere of inert gas, and take out after cooling to normal temperature. Isostatic pressing and heat treatment can reduce microcracks of the oxygen barrier layer, reduce porosity, release thermal stress, and improve compactness.
Example 1
A niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure comprises a substrate, a transition layer and an oxygen barrier layer, wherein the substrate is roughened by laser.
The preparation method of the laser coarsening structure in the niobium-tungsten alloy antioxidant coating structure comprises the following steps:
and carrying out laser roughening treatment on the matrix by using an ultraviolet nanosecond laser, wherein the laser frequency of the ultraviolet nanosecond laser is 30kHz, the power is 9w, the etching frequency is 10 times, the etching rate is 100mm/s, and etching of longitudinal stripes is carried out. The depth of the stripes was 15 μm and the pitch was 200. mu.m. And placing the coarsened niobium-tungsten alloy in 98% concentrated sulfuric acid for ultrasonic cleaning for 30min, placing the alloy in a saturated sodium hydroxide aqueous solution for ultrasonic cleaning for 30min to remove oxides generated on the surface, placing the alloy in deionized water for ultrasonic cleaning for 15min, and finally placing the alloy in absolute ethyl alcohol for ultrasonic cleaning for 15 min.
The preparation method of the transition layer in the niobium-tungsten alloy antioxidant coating structure comprises the following steps:
ta powder is added into a plastic container containing HF (the concentration is about 40 percent) solution, and the mixture is heated in a closed bin with exhaust equipment in a water bath at about 80 ℃, wherein the mass ratio of HF acid to Ta powder is about 1.5. In the experimental process, Ta powder is rapidly dissolved, and gas is emitted at the same time. Filtering after the reaction is finished to obtain TaF5The solution was dried in an oven at 120 ℃ to give a white powder. Mixing white powder and graphite powder according to the proportion of 1: 1 mass ratio, wrapping the niobium-tungsten matrix, and then placing the niobium-tungsten matrix in an Ar protective atmosphere furnace for high-temperature heat treatment at 1800 ℃ for about 1h, wherein the heating rate is 10 ℃/min.
The method for forming the oxygen barrier layer in the niobium-tungsten alloy anti-oxidation coating structure comprises the following steps:
respectively refining hafnium carbide powder, zirconium carbide powder and zirconium oxide powder by ball milling, adjusting the mass ratio of the hafnium carbide powder, the zirconium carbide powder and the zirconium oxide powder according to the content of the components, then spraying the powder on the outer layer of the transition layer by a plasma spraying machine under the control of the spraying distance of 150mm, the spraying power of 30kW and the powder feeding speed of 3kg/h to prepare the oxygen barrier layer of the niobium-tungsten alloy.
The anti-oxidation coating is subjected to cold isostatic pressing treatment and then is subjected to an annealing process, and the method comprises the following steps:
putting the niobium-tungsten alloy into a vacuum bag, vacuumizing and sealing, putting the vacuum bag into a cold isostatic press for isostatic pressing at 30MPa for 15 minutes, taking out the vacuum bag, drying, putting the vacuum bag into a high-temperature atmosphere furnace, carrying out heat preservation treatment at 800 ℃ for 1 hour at the heating rate of 5 ℃/min under the protection of argon, naturally cooling to room temperature, and taking out the vacuum bag to finish the annealing process.
Example 2
A niobium-tungsten alloy ultrahigh-temperature oxidation resistant coating structure is characterized in that niobium-tungsten alloy is firstly placed in 98% concentrated sulfuric acid to be subjected to ultrasonic cleaning for 30min, then placed in a saturated sodium hydroxide aqueous solution to be subjected to ultrasonic cleaning for 30min so as to remove oxides generated on the surface, then placed in deionized water to be subjected to ultrasonic cleaning for 15min, and finally placed in absolute ethyl alcohol to be subjected to ultrasonic cleaning for 15 min.
The preparation method of the transition layer in the niobium-tungsten alloy antioxidant coating structure comprises the following steps:
ta powder is added into a plastic container containing HF (the concentration is about 40 percent) solution, and the mixture is heated in a closed bin with exhaust equipment in a water bath at about 80 ℃, wherein the mass ratio of HF acid to Ta powder is about 1.5. In the experimental process, Ta powder is rapidly dissolved, and gas is emitted at the same time. Filtering after the reaction is finished to obtain TaF5The solution was dried in an oven at 120 ℃ to give a white powder. Mixing the white powder and graphite powder according to the mass ratio of 1: 1, wrapping the niobium-tungsten matrix, and then placing the niobium-tungsten matrix in an Ar protective atmosphere furnace for high-temperature heat treatment at 1800 ℃ for about 1h, wherein the heating rate is 10 ℃/min.
The method for forming the oxygen barrier layer in the niobium-tungsten alloy anti-oxidation coating structure comprises the following steps:
respectively refining hafnium carbide powder, zirconium carbide powder and zirconium oxide powder by ball milling, adjusting the mass ratio of the hafnium carbide powder, the zirconium carbide powder and the zirconium oxide powder according to the content of the components, controlling the spraying distance to be 150mm by a plasma spraying machine, controlling the spraying power to be 30kW and controlling the powder feeding rate to be 3kg/h, and spraying the powder on the outer layer of the transition layer to prepare the oxygen barrier layer of the niobium-tungsten alloy.
The anti-oxidation coating is subjected to cold isostatic pressing and annealing process, and the method is specifically carried out as follows:
putting the niobium-tungsten alloy into a vacuum bag, vacuumizing and sealing, putting the vacuum bag into a cold isostatic press for isostatic pressing at 30MPa for 15 minutes, taking out the vacuum bag, drying, putting the vacuum bag into a high-temperature atmosphere furnace, carrying out heat preservation treatment at 800 ℃ for 1 hour at the heating rate of 5 ℃/min under the protection of argon, taking out the vacuum bag after naturally cooling to the normal temperature, and finishing the annealing process.
Table 1 lists the thermal test results before and after laser roughening of the niobium-tungsten alloy oxidation resistant coatings of examples 1 and 2.
Figure BDA0002305791620000091
TABLE 1
The difference between example 1 and example 2 is that example 1 was subjected to laser roughening treatment, and example 2 was not subjected to laser roughening treatment. As can be seen from the table above, the thermal shock resistance of the substrate with the anti-oxidation coating prepared after laser roughening treatment is remarkably improved.
The invention can be realized by all the raw materials listed in the invention, and can be realized by the upper and lower limit values and interval values of all the raw materials, and can be realized by the upper and lower limit values and interval values of the process parameters (such as pressure, temperature, time, heating rate and the like) listed in the invention, but the examples are not listed.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The utility model provides a niobium tungsten alloy superhigh temperature antioxidation coating structure which characterized in that, this structure includes:
the surface of the niobium-tungsten alloy matrix is subjected to laser roughening treatment;
and the niobium-tungsten alloy anti-oxidation coating is attached to the surface of the niobium-tungsten alloy matrix roughened by the laser.
2. The niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure as claimed in claim 1, wherein the laser roughening treatment is performed to obtain transverse/longitudinal stripes with a depth of 10 to 50 μm and an interval of 50 to 200 μm.
3. The niobium tungsten alloy ultra high temperature oxidation resistant coating structure of claim 1 or 2, wherein the niobium tungsten alloy oxidation resistant coating comprises: the niobium-tungsten alloy oxidation-resistant coating comprises a transition layer and an oxygen barrier layer, wherein the transition layer is positioned on the surface of the niobium-tungsten alloy substrate, the oxygen barrier layer is positioned on the surface of the transition layer, and the niobium-tungsten alloy oxidation-resistant coating is subjected to densification treatment.
4. The niobium tungsten alloy ultra-high temperature oxidation resistant coating structure of claim 3, wherein the transition layer material has a coefficient of thermal expansion between the materials selected for the niobium tungsten alloy and the oxygen barrier layer.
5. The niobium-tungsten alloy ultrahigh temperature oxidation resistant coating structure as claimed in any one of claims 1 to 4, wherein the transition layer is a thin film layer with a thickness of 10 to 60 μm.
6. The niobium tungsten alloy ultra-high temperature oxidation resistant coating structure as claimed in any one of claims 1 to 5, wherein the transition layer is one of silicon carbide, molybdenum silicide, tungsten carbide, tantalum, niobium silicide or magnesium oxide.
7. The niobium tungsten alloy ultra high temperature oxidation resistant coating structure of any one of claims 1 to 6, wherein the oxygen barrier layer is a composite coating with a thickness of more than 60 μm and less than 200 μm.
8. The niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure as recited in any one of claims 1 to 7, wherein the oxygen barrier layer is at least one of titanium oxide, haar oxide, magnesium oxide, hafnium carbide, tantalum carbide, silicon carbide, zirconium boride.
9. A method for preparing the niobium-tungsten alloy ultra-high temperature oxidation resistant coating structure as claimed in any one of claims 1 to 8, which comprises the following steps:
s1, carving stripes on the niobium-tungsten alloy through a laser;
s2, preparing a transition layer on the surface of the niobium-tungsten alloy substrate;
s3, preparing an oxygen barrier layer on the surface of the transition layer;
and S4, performing densification treatment on the prepared niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating.
10. The method of claim 9, wherein the transition layer and the oxygen barrier layer are densified using an isostatic and annealing process.
CN201911239360.6A 2019-12-06 2019-12-06 Niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and preparation method thereof Pending CN110863167A (en)

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