CN114574834A - Ta-Re layered composite material and preparation method and application thereof - Google Patents
Ta-Re layered composite material and preparation method and application thereof Download PDFInfo
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- CN114574834A CN114574834A CN202111458339.2A CN202111458339A CN114574834A CN 114574834 A CN114574834 A CN 114574834A CN 202111458339 A CN202111458339 A CN 202111458339A CN 114574834 A CN114574834 A CN 114574834A
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims description 41
- 230000008021 deposition Effects 0.000 claims description 41
- 238000005229 chemical vapour deposition Methods 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001020 plasma etching Methods 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000003486 chemical etching Methods 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003870 refractory metal Substances 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005660 chlorination reaction Methods 0.000 description 12
- 238000001994 activation Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- RXPRRQLKFXBCSJ-GIVPXCGWSA-N vincamine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C[C@](O)(C(=O)OC)N5C2=C1 RXPRRQLKFXBCSJ-GIVPXCGWSA-N 0.000 description 1
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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
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
-
- 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
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
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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
- 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
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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
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- 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
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- 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
- C23C16/56—After-treatment
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a Ta-Re layered composite material and a preparation method and application thereof, belonging to the field of composite materials. The invention provides a Ta-Re layered composite material, which comprises a Ta matrix layer and a Re reinforcing layer which are arranged in a stacked mode. Based on the performance advantages of metal Ta and Re, the novel light high-strength Ta-Re layered composite material is prepared by taking the relatively light and cheap refractory metal Ta as a substrate and taking the high-melting-point high-strength Re as a strengthening layer, and the advantages of high strength Re and light weight Ta can be simultaneously considered, so that the structural material for the high-performance aerospace engine nozzle is obtained.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a Ta-Re layered composite material and a preparation method and application thereof.
Background
The jet pipe of the space flight engine is a key component on a thrust engine of a spacecraft such as a manned spacecraft, a lunar exploration satellite and the like, is an important component of the spacecraft, and the performance of the jet pipe mainly depends on the ultra-high temperature resistance (the working temperature exceeds 1600 ℃). Is usually prepared by refractory rare and precious metals (Nb, Re, Mo, Ta, etc.). However, with the rapid development of aerospace technology, the traditional refractory metals which have higher requirements on the high-temperature characteristics and mechanical properties of the nozzle materials of aerospace engines cannot meet the requirements.
Rhenium (Re) is a rare metal with high melting point (3340 ℃), high strength, creep resistance and stable chemical properties, and is an important material for preparing the jet pipe of the aerospace engine. In the prior art, the Ir/Re material (taking Re as a substrate and Ir as a protective coating) prepared by Chemical Vapor Deposition (CVD) has the highest working temperature of 2200 ℃ and does not lose efficacy after continuous operation for 15 hours, and the Ir/Re material is successfully applied to a satellite attitude control engine and pushes the performance of a spray pipe material to a new height. Although Re has excellent high temperature strength and creep resistance, it also has the disadvantage of high density. How to ensure that the nozzle material has good high-temperature performance, and can reduce the weight (light weight) of the nozzle material, and the nozzle material has important significance for improving the effective load and the quick response of the spacecraft.
Disclosure of Invention
In view of the above, the present invention aims to provide a Ta-Re layered composite material, and a preparation method and an application thereof. The Ta-Re layered composite material provided by the invention has the advantage of light weight.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a Ta-Re layered composite material, which comprises a Ta matrix layer and a Re reinforcing layer which are arranged in a stacked manner.
Preferably, the volume fraction of the Re strengthening layer in the Ta-Re layered composite material is 10-50%.
The invention also provides a preparation method of the Ta-Re layered composite material, which comprises the following steps:
carrying out first chemical vapor deposition on Ta, chlorine and hydrogen on the surface of a Mo substrate under the vacuum condition to form a Ta deposition layer;
carrying out plasma etching activation treatment on the Ta deposition layer to form a Ta base layer;
carrying out second chemical vapor deposition on Re and chlorine on the surface of the Ta matrix layer under a vacuum condition to form a Re layer, and then carrying out Mo substrate separation to obtain a Ta/Re composite layer;
and carrying out heat treatment on the Ta/Re composite layer to obtain the Ta-Re layered composite material.
Preferably, the flow rate of the chlorine gas during the first chemical vapor deposition and the flow rate of the chlorine gas during the second chemical vapor deposition are respectively 50-80 mL/min, and the flow rate of the hydrogen gas during the first chemical vapor deposition is 400-600 mL/min.
Preferably, the Ta is preheated, and the preheating temperature is 1150-1350 ℃.
Preferably, the power of the plasma etching activation treatment is 1-5 kW, the hydrogen flow is 200-800 mL/s, the argon flow is 6-15 mL/s, the etching time is 5-60 min, and the etching temperature is 900 ℃.
Preferably, the Ta matrix layer further comprises preheating before the second chemical vapor deposition, and the preheating temperature is 1150-1350 ℃.
Preferably, the heat treatment temperature is 1400-1800 ℃, and the heat preservation time is 1-20 h.
Preferably, the Mo substrate is separated into wire cutting and/or chemical etching.
The invention also provides the application of the Ta-Re layered composite material in the structural material for the jet pipe of the aerospace engine.
The invention provides a Ta-Re layered composite material, which comprises a Ta matrix layer and a Re reinforcing layer which are arranged in a stacked mode. Based on the performance advantages of metal Ta and Re, the novel light high-strength Ta-Re layered composite material is prepared by taking the relatively light and cheap refractory metal Ta as a substrate and taking the high-melting-point high-strength Re as a strengthening layer, and the advantages of high strength Re and light weight Ta can be simultaneously considered, so that the structural material for the high-performance aerospace engine nozzle is obtained.
The invention also provides a preparation method of the Ta-Re layered composite material, which comprises the following steps: carrying out first chemical vapor deposition on Ta, chlorine and hydrogen on the surface of a Mo substrate under the vacuum condition to form a Ta deposition layer; carrying out plasma etching activation treatment on the Ta deposition layer to form a Ta base layer; carrying out second chemical vapor deposition on Re and chlorine on the surface of the Ta matrix layer under a vacuum condition to form a Re layer, and then carrying out Mo substrate separation to obtain a Ta/Re composite layer; and carrying out heat treatment on the Ta/Re composite layer to obtain the Ta-Re layered composite material.
In the invention, Chemical Vapor Deposition (CVD) is a technology for generating solid substances by utilizing gaseous precursor reactants through an atomic and intermolecular chemical reaction path, can greatly reduce the preparation temperature of Re and Ta, can obtain high-purity and compact Re and Ta materials by optimizing and controlling a deposition process, and is particularly suitable for preparing complex devices, films and coatings. However, because the layered composite material has a Ta and Re heterogeneous interface, and Ta and Re have great difference in physical and chemical properties (such as strength, plastic toughness, elastic modulus, thermal conductivity and the like), if the layered material is prepared by adopting the traditional chlorinated CVD process, the defects of easy cracking, low bonding strength, poor thermal conductivity and the like are easy to occur at the Ta/Re interface, the invention provides a chlorinated Chemical Vapor Deposition (CVD) preparation technology of the Ta-Re layered composite material combined with the plasma etching activation process, the surface activity of the Ta layer is improved by plasma etching, the chemical reaction between the Re layer and the Ta layer is accelerated, so that the problems of easy cracking of the interface, low bonding strength and poor thermal conductivity of the Ta-Re layered composite material prepared by the traditional Chemical Vapor Deposition (CVD) are effectively solved, the room-temperature mechanical property of the Ta-Re layered composite material is improved by 15 percent, the high temperature stability is also improved obviously, and the Ta-Re interface is combined firmly.
Compared with the prior art, the preparation method has the following beneficial effects:
the chlorination reaction and the deposition reaction of the raw materials Ta and Re are carried out simultaneously, the reaction process is simple, the deposition reaction temperature is higher, and impurity pollution is avoided;
the plasma etching activation treatment process can solve the problems of easy cracking, poor associativity, large difference in physical and chemical properties and the like of a Ta/Re heterogeneous interface of the layered composite material, and greatly improves the strength and high-temperature creep resistance of the Ta/Re layered composite material;
because the gas is used in the deposition reaction, the product purity is high, the grain structure is refined, the grain growth can be still resisted at high temperature, the density of the deposited material is high, and the density is close to the theoretical density. According to the thermodynamic principle, the direction with the lowest thermodynamic energy is selected for the growth of the Ta and Re coating, and the coating forms a texture structure with preferred orientation;
the CVD deposition of the Ta-Re layered composite material is carried out at a high temperature of 1150-1350 ℃, the Ta-Re interface generates element diffusion reaction in the deposition process to form metallurgical bonding, the bonding between the interfaces is firm, after heat treatment, the highest room temperature tensile strength is 845Mpa, the maximum elongation is 24%, the density can reach 99.6% of the theoretical density, and the Ta-Re layered composite material can be used as a refractory metal device applied to a jet pipe of an aerospace engine and other high-temperature fields;
the adopted CVD deposition device has low investment, simple and easily-controlled deposition process, high utilization rate of raw materials and stable quality of the Ta-Re layered composite material.
Detailed Description
The invention provides a preparation method of a Ta-Re layered composite material, which comprises a Ta matrix layer and a Re reinforcing layer which are arranged in a stacked mode.
In the present invention, the volume fraction of the Re reinforcement layer in the Ta — Re layered composite material is preferably 10% to 50%, more preferably 20% to 40%, most preferably 10%, 20%, 30%, 40% or 50%.
The invention also provides a preparation method of the Ta-Re layered composite material, which comprises the following steps:
carrying out first chemical vapor deposition on Ta, chlorine and hydrogen on the surface of a Mo substrate under the vacuum condition to form a Ta deposition layer;
carrying out plasma etching activation treatment on the Ta deposition layer to form a Ta base layer;
carrying out second chemical vapor deposition on Re and chlorine on the surface of the Ta matrix layer under a vacuum condition to form a Re layer, and then carrying out Mo substrate separation to obtain a Ta/Re composite layer;
and carrying out heat treatment on the Ta/Re composite layer to obtain the Ta-Re layered composite material.
According to the invention, Ta, chlorine and hydrogen are subjected to first chemical vapor deposition on the surface of a Mo substrate under a vacuum condition to form a Ta deposition layer.
In the present invention, the first chemical vapor deposition is preferably carried out in a vertical tube reactor. In the present invention, the vertical tube reactor preferably includes a chlorination chamber and a deposition chamber.
In the present invention, the Ta is preferably a Ta plate, and the purity of the Ta plate is preferably 99.95%; the Mo substrate is preferably a rectangular parallelepiped molybdenum block.
In the invention, the cuboid molybdenum block is preferably subjected to polishing, acid washing, ultrasonic cleaning and drying treatment in sequence before use, and the specific modes of the polishing, acid washing, ultrasonic cleaning and drying treatment are not particularly limited and can be realized by adopting a mode known by a person skilled in the art. The method preferably comprises the steps of installing the cuboid molybdenum block on a rotating platform of a deposition chamber, placing the Ta plate in a chlorination chamber, determining the placing amount of the Ta plate according to the area and the thickness of a coating to be deposited, sealing the vertical tubular reactor, and pumping the vertical tubular reactor to be in a vacuum state, wherein the vacuum degree of the vacuum state is not lower than 1.0 Pa.
In the present invention, the purity of the hydrogen gas is preferably 99.95%, and the purity of the chlorine gas is preferably 99.60%.
In the invention, the Ta is preferably preheated, and the preheating temperature is preferably 1150-1350 ℃, and more preferably 1200 ℃.
In the invention, the flow rate of hydrogen in the first chemical vapor deposition is preferably 400-600 mL/min, and the flow rate of chlorine is preferably 50-80 mL/min.
In the present invention, the pressure of the deposition chamber at the time of the first chemical vapor deposition is preferably 1000 Pa.
In the present invention, the chemical reaction in the first chemical vapor deposition process is as follows:
2Ta(s)+5Cl2(g)→2TaCl5(g)
2TaCl5(g)+5H2(g)→2Ta(s)+10HCl(g)
in the invention, Ta and chlorine gas are subjected to chlorination reaction, and the chlorination reaction temperature is preferably 200-300 ℃, and more preferably 250 ℃.
After the Ta deposition layer is formed, the invention carries out plasma etching activation treatment on the Ta deposition layer to form a Ta base layer. In the invention, the plasma etching activation treatment has the effect that more Ta vacancies can appear on the surface of a Ta deposition layer, so that the surface activity of Ta can be effectively increased, the chemical reaction on the surface of a coating is accelerated, the subsequent deposition of a Re layer is facilitated, and the bonding performance of a Ta-Re heterogeneous interface is further improved.
In the invention, the plasma etching activation treatment preferably uses hydrogen atoms as etching atoms and argon as energy-carrying ions, on one hand, the hydrogen plasma bombards the surface of the Ta deposition layer to enable the Ta atoms on the surface to be sputtered, and because the atomic weight of Ar is large, ionization is more likely to occur, and during the collision process of the mixed gas of argon and hydrogen, the ionized Ar ions can promote H2The ionization of the hydrogen plasma increases the density of the hydrogen plasma, accelerates the bombardment and reduction process of the hydrogen plasma, enhances the desorption of etching products and the reaction of the hydrogen ions and the surface under the etching action of the hydrogen and argon mixed plasma, and improves the etching strength.
In the present invention, the purity of the argon gas is preferably 99.95%.
In the invention, the power of the plasma etching activation treatment is preferably 1-5 kW, more preferably 2kW, the hydrogen flow is preferably 200-800 mL/s, more preferably 500mL/s, the argon flow is preferably 6-15 mL/s, the etching time is preferably 5-60 min, more preferably 10min, and the etching temperature is preferably 900 ℃.
After the Ta base layer is formed, the invention carries out second chemical vapor deposition on Re and chlorine on the surface of the Ta base layer under the vacuum condition to form a Re layer, and then carries out Mo substrate separation to obtain a Ta/Re composite layer.
In the invention, the Ta base layer preferably further comprises preheating before the second chemical vapor deposition, and the preheating temperature is preferably 1150-1350 ℃, and more preferably 1200 ℃.
In the present invention, the Re is preferably a Re plate.
According to the invention, the Ta substrate layer is preferably arranged on a rotary platform of a deposition chamber, the Re plate is arranged in a chlorination chamber, the arrangement amount of the Re plate is determined according to the required deposition area and thickness, then the vertical tubular reactor is sealed and pumped into a vacuum state, and the vacuum degree of the vacuum state is not lower than 1.0 Pa.
In the invention, the Re and chlorine gas are subjected to chlorination reaction, and the temperature of the chlorination reaction is preferably 200-300 ℃, and more preferably 250 ℃.
In the invention, the flow rate of the chlorine gas during the second chemical vapor deposition is preferably 50-80 mL/min.
In the present invention, the pressure of the deposition chamber in the second chemical vapor deposition is preferably 1000 Pa.
In the present invention, the chemical reaction in the second chemical vapor deposition process is as follows:
2Re(s)+5Cl2(g)→2ReCl5(g)
2ReCl5(g)→2Re(s)+5Cl5(g)
in the present invention, the Mo substrate separation is preferably wire cutting and/or chemical etching. The present invention is not limited to the specific manner of wire cutting and chemical etching, and may be implemented in a manner known to those skilled in the art.
After the Ta/Re composite layer is obtained, the Ta/Re composite layer is subjected to heat treatment to obtain the Ta-Re layered composite material. In the present invention, the heat treatment serves to remove residual stress during deposition and to achieve uniform texture.
In the invention, the heat treatment temperature is preferably 1400-1800 ℃, more preferably 1600 ℃, and the heat preservation time is preferably 1-20 h, more preferably 4-6 h.
The invention also provides the application of the Ta-Re layered composite material in the structural material for the jet pipe of the aerospace engine. The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
In order to further illustrate the present invention, the Ta — Re layered composite material, the preparation method thereof, and the rhenium lance provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The Ta-Re laminated composite material comprises a Ta base layer and a Re reinforcing layer which are arranged in a laminated mode, wherein the volume fraction of the Re reinforcing layer is 20%, and the total thickness of the composite material is 1 mm.
The preparation method comprises the following steps:
processing a cuboid molybdenum block into a molybdenum plate with a required size, and polishing, pickling, ultrasonically cleaning and drying the surface of the cuboid molybdenum block; the rectangular molybdenum block is arranged on a rotating platform of the deposition chamber and is positioned in the middle of the induction coil; placing a Ta plate in the quartz periphery of a chlorination chamber, sealing a deposition system and vacuumizing to 0.8 Pa; the chlorination chamber is heated to 250 ℃ and the rectangular molybdenum block is heated to 1200 ℃. Then hydrogen gas is respectively introduced into the deposition chamber at a rate of 400mL/min and chlorine gas is introduced into the deposition chamber at a rate of 50mL/min, the pressure of the deposition chamber is adjusted to 1000Pa, and the deposition preparation of the Ta layer is started; after the test is carried out for 8 hours, the deposition is stopped, and the deposition of the Ta layer is completed; carrying out plasma etching activation treatment on the Ta deposition layer by adopting high-power microwave plasma chemical vapor deposition (PMCVD) equipment, wherein the etching power is 2kW, the hydrogen is 500mL/s, the argon is 15mL/s, the etching time is 10min, and the etching temperature is 900 ℃; installing the activated Ta deposition layer sample on a rotating platform of a deposition chamber, placing a Re plate in the quartz periphery of a chlorination chamber, sealing the deposition system and vacuumizing to 0.8 Pa; the chlorination chamber was heated to 250 ℃ and the Ta deposit sample was heated to 1200 ℃. Then chlorine gas is respectively introduced into the chambers at a rate of 50mL/min, and the pressure of the deposition chamber is adjusted to 1000 Pa; after the test is carried out for 4 hours, the deposition process is stopped, the deposition of the Re layer is completed, and the cuboid molybdenum block and the deposition material (Ta/Re composite layer) are separated by adopting a linear cutting and chemical corrosion method; and carrying out high-temperature vacuum heat treatment on the Ta/Re composite layer at 1600 ℃ for 4 h.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.7%, the tensile strength at room temperature is 540MPa, and the elongation is 24%.
Example 2
The Ta-Re laminated composite material is prepared by laminating a Ta matrix layer and an Re reinforcing layer, wherein the volume fraction of the Re reinforcing layer is 30%, the total thickness of the composite material is 1mm, the thickness of the Re reinforcing layer is 0.3mm, and the thickness of the Ta matrix layer is 0.7 mm.
The preparation method is the same as that of example 1.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.6%, the room-temperature tensile strength is 590Mpa, and the elongation is 18%.
Example 3
The Ta-Re laminated composite material is prepared by laminating a Ta matrix layer and an Re reinforcing layer, wherein the volume fraction of the Re reinforcing layer is 40%, the total thickness of the composite material is 1mm, the thickness of the Re reinforcing layer is 0.4mm, and the thickness of the Ta matrix layer is 0.6 mm.
The preparation method is the same as that of example 1.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.6%, the tensile strength at room temperature is 620Mpa, and the elongation is 15%.
Example 4
The Ta-Re laminated composite material is prepared by laminating a Ta matrix layer and an Re reinforcing layer, wherein the volume fraction of the Re reinforcing layer is 50%, the total thickness of the composite material is 1mm, the thickness of the Re reinforcing layer is 0.5mm, and the thickness of the Ta matrix layer is 0.5 mm.
The preparation method is the same as that of example 1.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.5%, the room-temperature tensile strength is 845Mpa, and the elongation is 12%.
Example 5
The Ta-Re laminated composite material comprises a Ta base layer and a Re reinforcing layer which are arranged in a laminated mode, wherein the volume fraction of the Re reinforcing layer is 20%, the total thickness of the composite material is 2mm, the thickness of the Re reinforcing layer is 0.4mm, and the thickness of the Ta base layer is 1.6 mm.
The preparation method is the same as example 1, except that high-temperature vacuum heat treatment at 1600 ℃ for 6 hours is carried out.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.5%, the room-temperature tensile strength is 570Mpa, and the elongation is 24%.
Example 6
The Ta-Re laminated composite material comprises a Ta base layer and a Re reinforcing layer which are arranged in a laminated mode, wherein the volume fraction of the Re reinforcing layer is 30%, the total thickness of the composite material is 2mm, the thickness of the Re reinforcing layer is 0.6mm, and the thickness of the Ta base layer is 1.4 mm.
The preparation method is the same as example 1, except that high-temperature vacuum heat treatment at 1600 ℃ for 6 hours is carried out.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.6%, the tensile strength at room temperature is 645MPa, and the elongation is 17%.
Example 7
The Ta-Re laminated composite material is prepared by laminating a Ta matrix layer and an Re reinforcing layer, wherein the volume fraction of the Re reinforcing layer is 40%, the total thickness of the composite material is 2mm, the thickness of the Re reinforcing layer is 0.8mm, and the thickness of the Ta matrix layer is 1.2 mm.
The preparation method is the same as example 1, except that high-temperature vacuum heat treatment at 1600 ℃ for 6 hours is carried out.
The obtained Ta-Re layered composite material is subjected to related detection, the relative density is 99.6%, the room-temperature tensile strength is 670Mpa, and the elongation is 14%.
In conclusion, with the increase of the volume percentage content of the Re strengthening layer, the room-temperature tensile strength of the Ta-Re layered composite material is increased, but the elongation is reduced; after heat treatment, there was an approximately 10% increase in room temperature tensile strength with a small increase in elongation.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A Ta-Re layered composite material is characterized by comprising a Ta matrix layer and a Re reinforcing layer which are arranged in a stacked mode.
2. The Ta-Re layered composite of claim 1 wherein the volume fraction of the Re reinforcing layer in the Ta-Re layered composite is 10% to 50%.
3. A method of producing a Ta-Re layered composite according to claim 1 or 2, characterized by comprising the steps of:
carrying out first chemical vapor deposition on Ta, chlorine and hydrogen on the surface of a Mo substrate under the vacuum condition to form a Ta deposition layer;
carrying out plasma etching activation treatment on the Ta deposition layer to form a Ta base layer;
carrying out second chemical vapor deposition on Re and chlorine on the surface of the Ta matrix layer under a vacuum condition to form a Re layer, and then carrying out Mo substrate separation to obtain a Ta/Re composite layer;
and carrying out heat treatment on the Ta/Re composite layer to obtain the Ta-Re layered composite material.
4. The method according to claim 3, wherein the flow rates of the chlorine gas and the hydrogen gas in the first and second chemical vapor depositions are independently 50 to 80mL/min and 400 to 600mL/min, respectively.
5. The method according to claim 3, wherein the Ta is preheated at a temperature of 1150-1350 ℃.
6. The preparation method according to claim 3, wherein the power of the plasma etching activation treatment is 1-5 kW, the hydrogen flow is 200-800 mL/s, the argon flow is 6-15 mL/s, the etching time is 5-60 min, and the etching temperature is 900 ℃.
7. The method according to claim 3, wherein the Ta matrix layer further comprises a pre-heat temperature of 1150-1350 ℃ before the second chemical vapor deposition.
8. The preparation method according to claim 3, wherein the heat treatment temperature is 1400-1800 ℃ and the holding time is 1-20 h.
9. The method of claim 3, wherein the Mo substrate separation is wire cutting and/or chemical etching.
10. Use of a Ta-Re layered composite according to claim 1 or 2 in structural materials for jet pipes of space engines.
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