CN109554707B - Ultra-limit aluminum alloy and preparation method thereof - Google Patents

Ultra-limit aluminum alloy and preparation method thereof Download PDF

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CN109554707B
CN109554707B CN201811640741.0A CN201811640741A CN109554707B CN 109554707 B CN109554707 B CN 109554707B CN 201811640741 A CN201811640741 A CN 201811640741A CN 109554707 B CN109554707 B CN 109554707B
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aluminum alloy
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CN109554707A (en
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冯晶
吴福硕
宋鹏
种晓宇
葛振华
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Kunming University of Science and Technology
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Priority to JP2021538453A priority patent/JP7242867B2/en
Priority to EP19903063.6A priority patent/EP3904555A4/en
Priority to US17/419,250 priority patent/US11530485B2/en
Priority to PCT/CN2019/117283 priority patent/WO2020134655A1/en
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Abstract

The invention belongs to the technical field of aluminum alloy metal materials, and discloses an ultra-limit aluminum alloy and a preparation method thereof, wherein the ultra-limit aluminum alloy comprises an aluminum alloy substrate, wherein a composite bonding layer, a composite ceramic layer, a reflecting layer, a catadioptric layer, an insulating layer and a foam carbon layer are sequentially deposited on the surface of the aluminum alloy substrate; the composite bonding layer comprises a bonding layer deposited on the surface of the aluminum alloy substrate and a noble metal layer deposited on the surface of the bonding layer; the composite ceramic layer comprises a ceramic A layer and a ceramic B layer. During preparation, the composite bonding layer, the composite ceramic layer, the reflecting layer, the catadioptric layer, the insulating layer and the foam carbon layer are deposited on the surface of the aluminum alloy in sequence, and the ultra-limit aluminum alloy is formed. The use temperature of the ultra-limit aluminum alloy provided by the invention is increased to be higher than the melting point of the original aluminum alloy by 100-500 ℃, and the ultra-limit aluminum alloy can be used at the ultra-limit temperature.

Description

Ultra-limit aluminum alloy and preparation method thereof
Technical Field
The invention belongs to the field of aluminum alloy metal materials, and particularly relates to an ultra-limit aluminum alloy and a preparation method thereof.
Background
Aluminum alloy is a non-ferrous metal structural material which is most widely applied in industry, has the excellent characteristics of low density, high strength, excellent plasticity, electrical conductivity, corrosion resistance and the like, is widely used in the fields of aviation, aerospace, automobiles, mechanical manufacturing, ships and chemical industry, and particularly plays an irreplaceable role in the field of aerospace. The usage amount of the high-strength aluminum alloy on the commercial aircraft with excellent comprehensive performance reaches more than 80% of the structural quality, so the high-strength aluminum alloy is generally regarded by the global aviation industry. Various aircraft have aluminum alloys as the primary structural material, and the skins, beams, ribs, stringers, bulkheads, and landing gear on the aircraft may be made from aluminum alloys.
With the development of technology and the practical requirements of society, the speed requirement of the aircraft is higher and higher, the speed increase of the aircraft means that the surface temperature of the aircraft is increased, and the melting point of the existing aluminum alloy is about 650 ℃, and the use temperature is about 70% of the melting point of the existing aluminum alloy, so that the use requirement of the aircraft after the speed increase cannot be met (the melting point temperature of the aluminum alloy is exceeded) at the ultra-limit temperature, and the use requirement of the aircraft after the speed increase is met, therefore, the use of the aluminum alloy is limited in the development process of the aircraft.
In the research process of increasing the flying speed of an aircraft, in order to adapt to the increase of the surface temperature of the aircraft, an alloy with a high melting point, such as an iron alloy, is generally used as a main structural material for manufacturing the aircraft, but in the actual research and development process, the weight of the iron alloy is found to be large, and the use of the iron alloy as the main structural material for manufacturing the aircraft can cause the weight of the aircraft to increase, but can cause the flying speed of the aircraft to slow down, so that the actual requirements cannot be met. If the aircraft is accelerated without changing the material, the service life of the aircraft can be shortened.
Disclosure of Invention
The invention aims to provide an ultra-limit aluminum alloy and a preparation method thereof, and aims to solve the problem that the aluminum alloy cannot be used at an ultra-limit temperature.
In order to achieve the purpose, the invention provides the following basic technical scheme that the ultra-limit aluminum alloy comprises an aluminum alloy substrate, wherein a composite bonding layer and a composite ceramic layer are sequentially deposited on the surface of the aluminum alloy substrate; the composite bonding layer comprises a bonding layer deposited on the surface of the aluminum alloy substrate and a noble metal layer deposited on the surface of the bonding layer; the composite ceramic layer comprises a ceramic A layer and a ceramic B layer.
The beneficial effects of the technical scheme are as follows:
through a great deal of research, the inventor develops an ultra-limit aluminum alloy which meets the requirement that the aluminum alloy is used at an ultra-limit temperature. In the development process, people generally consider that when the ambient temperature is higher than the use temperature of the alloy, the alloy cannot be used at the temperature, and therefore other high-melting-point alloys are required to be used, and the inventors do not go so far and try to improve the aluminum alloy to meet the requirements of aircraft manufacturing. In the process of continuous trial by the inventor, the inventor discovers that the use temperature of the aluminum alloy can be increased to be higher than the original melting point of 100-500 ℃ by depositing a coating with a certain proportion on the surface of the aluminum alloy, so that the use temperature of the aluminum alloy is greatly increased, and the requirement of manufacturing an aircraft is met; in a high-temperature environment, the use temperature of the aluminum alloy is difficult to be raised by 2-3 ℃, so that the research of the applicant is a great progress on the use of the aluminum alloy.
According to the technical scheme, the composite bonding layer and the composite ceramic layer are deposited on the aluminum alloy substrate, so that the service temperature of the aluminum alloy can be greatly improved, and the aluminum alloy is suitable for use at the temperature exceeding the limit temperature. The composite bonding layer is deposited, so that the bonding effect between each coating and the aluminum alloy matrix can be improved, and the coating is prevented from falling off in the using process. The composite ceramic layer is deposited, so that the heat conduction can be reduced, and the service temperature of the aluminum alloy matrix is improved. The reflecting layer has the effect of reflecting a heat source, so that the heat source on the surface of the aluminum alloy is reduced, and the use temperature is increased.
In summary, the present invention has the following technical effects:
1. the ultra-limit aluminum alloy provided by the invention has excellent high-temperature mechanical and chemical stability, can be used under the condition of exceeding the melting point of an aluminum alloy matrix, and enhances the application range.
2. According to the invention, the multi-layer coating is deposited on the surface of the aluminum alloy substrate, so that the use temperature of the aluminum alloy substrate can be raised to be higher than the melting point of the original aluminum alloy substrate by 100-500 ℃, and the use of the aluminum alloy in an ultra-limit environment is realized.
3. The ultra-limit aluminum alloy provided by the invention has excellent corrosion resistance, so that the service time under acidic or alkaline conditions is greatly prolonged, the waste caused by material corrosion can be reduced, and the cost is saved.
4. The method breaks through the limitation of the traditional idea that only the material can be replaced when the environmental temperature is higher than the use temperature of the material, and improves the use temperature of the material by depositing the coating on the surface of the material, so that the ultra-limit aluminum alloy can be suitable for the preparation of the accelerated aircraft, and the service life of the aircraft cannot be shortened.
Further, the thickness of the composite bonding layer is 100-200 μm, the thickness of the composite ceramic layer is 150-500 μm, and a reflecting layer with the thickness of 10-30 μm, a catadioptric layer with the thickness of 10-30 μm, an insulating layer with the thickness of 10-200 μm and a foam carbon layer with the thickness of 20-200 μm are sequentially deposited outside the composite ceramic layer.
Has the advantages that: the catadioptric layer is deposited on the composite ceramic layer, and can block the refraction of infrared rays in the coating, so that the temperature of the aluminum alloy substrate is reduced, and the service temperature of the prepared aluminum alloy is increased. The insulating layer can isolate the ionization generation on the surface of the aluminum alloy substrate and resist the erosion of charges to the substrate material. When in use, the carbon of the foam carbon layer is vaporized and cooled, and a vaporization film is formed on the surface of the aluminum alloy substrate, so that the heat transmission is further prevented, and the use temperature of the aluminum alloy is increased. According to the technical scheme, the service temperature of the aluminum alloy is greatly improved through the matching of the coatings. And the thickness of each coating is set, so that the service temperature of the prepared ultra-limit aluminum alloy is improved, the weight of the prepared ultra-limit aluminum alloy is slightly increased, and the ultra-limit aluminum alloy has the characteristic of light weight and is convenient for manufacturing aircrafts.
Furthermore, the bonding layer comprises one or a mixture of more of MCrAlY, NiAl, NiCr-Al and Mo, wherein the MCrAlY is NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY; the component of the noble metal layer is one or more of Au, Pt, Ru, Rh, Pd and Ir.
Has the advantages that: the proportions of elements in the three materials of NiCrCoAlY, NiCoCrAlY and CoNiCrAlY are different, so that the prepared materials are different. The bonding layer has good bonding effect, so that the subsequent coating and the aluminum alloy matrix have good bonding effect, and the falling probability of the coating is reduced; the noble metal has the characteristic of oxidation resistance, and can effectively prevent oxygen from diffusing into the bonding layer and the aluminum alloy substrate at high temperature, so that the oxidation resistance of the coating is improved, and the service life of the coating is prolonged.
Further, the ceramic A layer contains YSZ or rare earth zirconate (RE)2Zr2O7) (ii) a The component of the ceramic B layer is ZrO2-RETaO4。
Has the advantages that: YSZ or rare earth zirconate, a commonly used material as a thermal barrier coating, is readily available. ZrO (ZrO)2-RETaO4The low thermal conductivity can reduce the conduction of heat, so that the aluminum alloy matrix keeps low temperature in a high-temperature environment, thereby improving the service temperature of the prepared aluminum alloy; the high expansion coefficient is to match the thermal expansion coefficient of the bonding layer, and the thermal expansion coefficient of the noble metal bonding layer is also large, so that the noble metal bonding layer has high thermal expansion coefficientIn the thermal cycle process (namely the process of continuously heating and cooling), the thermal mismatch stress (stress generated by different thermal expansion coefficients) of the ceramic layer and the bonding layer is small, and the service life of the coating is further prolonged. (in a popular way, when two coatings with larger difference of thermal expansion coefficients are deposited together and the temperature is raised or lowered, the expansion degrees of the two coatings are seriously different, so that the stress between the two coatings is increased, and cracks or even falling-off is caused between the two coatings.)
Further, the ZrO2-RETaO4Is spherical and has a particle size of 10-70 μm.
Has the advantages that: when the ceramic B layer is deposited, the spraying effect is good, and the bonding effect of the ceramic B layer is good.
Further, the reflective layer has a composition of REVO4、RETaO4、Y2O3One or a mixture of several of them.
Has the advantages that: REVO4、RETaO4、Y2O3The reflection coefficient of (2) is high, so that the heat source can be reflected, the heat radiation is reduced, and the temperature of the aluminum alloy matrix is reduced, thereby improving the service temperature of the prepared aluminum alloy.
Furthermore, the component of the catadioptric layer is one or a mixture of two of graphene and boron carbide, and the spatial distribution of the graphene and the boron carbide is in a disordered arrangement state.
Has the advantages that: although graphene and boron carbide have higher refractive index, when incident light shines on the catadioptric layer, the refraction of light in all directions can be enhanced to the graphene and the boron carbide of unordered arrangement, avoids incident light to take place the refraction in same direction, reaches the dispersed effect of refraction, enters into the incident light intensity decline in the coating like this.
Further, the insulating layer is made of one or a mixture of epoxy resin, phenolic resin and ABS resin.
Has the advantages that: when the aircraft is used, the shell is rubbed with air and ionized, and the epoxy resin, the phenolic resin and the ABS resin can isolate conductive electrons and resist the erosion of charges to an aluminum alloy matrix.
The invention also provides another basic scheme, and the preparation method of the ultra-limit aluminum alloy comprises the following steps:
the method comprises the following steps:
firstly, depositing a bonding layer on the surface of an aluminum alloy substrate, and then depositing a noble metal layer on the surface of the bonding layer, so that the bonding layer and the noble metal layer form a composite bonding layer, wherein the total thickness of the composite bonding layer is 100-;
step two:
depositing a ceramic layer A and a ceramic layer B on the surface of the noble metal layer to form a composite ceramic layer, wherein the total thickness of the composite ceramic layer is 150-500 mu m;
step three:
depositing a reflecting layer on the surface of the composite ceramic layer, wherein the thickness of the reflecting layer is 10-30 mu m;
step four:
coating a catadioptric layer with a thickness of 10-30 μm on the surface of the reflecting layer;
step five:
coating an insulating layer on the surface of the catadioptric layer, wherein the thickness of the insulating layer is 10-200 mu m;
step six:
and coating a foam carbon layer on the surface of the insulating layer, wherein the thickness of the foam carbon layer is 20-200 mu m, so that the ultra-limit aluminum alloy is formed.
The beneficial effects of this technical scheme do:
by controlling the thickness of each coating deposited on the aluminum alloy substrate, the service temperature of the prepared ultra-limit aluminum alloy can be increased to 100-500 ℃ higher than the melting point of the original aluminum alloy, and the prepared ultra-limit aluminum alloy has excellent corrosion resistance. Meanwhile, the situation that the weight of the prepared ultra-limit aluminum alloy is increased greatly due to the fact that the thickness of the coating is large can be avoided, so that the ultra-limit aluminum alloy can keep the light characteristic and can be used at the ultra-limit temperature, and the use requirement of the existing aircraft for speed increase is met.
Further, in the first step, before the bonding layer is deposited, oil stains on the surface of the aluminum alloy substrate are removed; and shot blasting the surface of the aluminum alloy matrix to ensure that the surface roughness of the aluminum alloy matrix is 60-100 mu m.
Has the advantages that: the bonding effect between the aluminum alloy matrix and the coating can be improved by removing oil stains on the surface of the aluminum alloy matrix. The coating can generate larger internal stress in the process of curing, and the roughness of the surface of the aluminum alloy substrate after shot blasting can effectively eliminate the problem of stress concentration, so that the coating can be prevented from cracking. And the existence of the surface roughness can support the quality of a part of coating, which is beneficial to eliminating the sagging phenomenon.
Drawings
FIG. 1 is a schematic structural view of an ultra-limited aluminum alloy of the present invention;
FIG. 2 is a graph showing creep tests at 900 ℃ under 50MPa in example 1 of the present invention and in comparative example 13;
FIG. 3 is a graph showing the results of the salt spray corrosion test in example 1 of the present invention and comparative example 13.
Detailed Description
The following is further detailed by way of specific embodiments:
reference numerals in the drawings of the specification include: the composite ceramic light-emitting diode comprises an aluminum alloy substrate 1, a composite bonding layer 2, a bonding layer 21, a precious metal layer 22, a composite ceramic layer 3, a ceramic A layer 31, a ceramic B layer 32, a reflecting layer 4, a catadioptric layer 5, an insulating layer 6 and a carbon foam layer 7.
The invention provides an ultra-limit aluminum alloy, which comprises an aluminum alloy substrate 1, wherein a composite bonding layer 2 with the thickness of 100-200 mu m, a composite ceramic layer 3 with the thickness of 150-500 mu m, a reflecting layer 4 with the thickness of 10-30 mu m, a catadioptric layer 5 with the thickness of 10-30 mu m, an insulating layer 6 with the thickness of 10-200 mu m and a foam carbon layer 7 with the thickness of 20-200 mu m are sequentially deposited on the surface of the aluminum alloy substrate 1 as shown in figure 1. The composite bonding layer 2 comprises a bonding layer 21 deposited on the surface of the aluminum alloy substrate 1 and a precious metal layer 22 deposited on the surface of the bonding layer 21, the bonding layer 21 is a mixture of one or more of MCrAlY, NiAl, NiCr-Al and Mo, the MCrAlY is NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY, and the precious metal layer 22 is an alloy of one or more of Au, Pt, Ru, Rh, Pd and Ir; the composite ceramic layer 3 comprises a ceramic A layer 31 and a ceramicA ceramic B layer 32, a ceramic A layer 31 adjacent to the noble metal layer 22 or a ceramic B layer 32 adjacent to the noble metal layer 22, the ceramic A layer 31 being composed of YSZ or rare earth zirconate (RE)2Zr2O7RE ═ Y, Nd, Eu, Gd, Dy, Sm), the component of the ceramic B layer 32 is ZrO2-RETaO4，ZrO2-RETaO4Is spherical, has a particle diameter of 10-70 μm and has a chemical formula of RE1-x(Ta/Nb)1-x(Zr/Ce/Ti)2xO4RE ═ Y, Nd, Eu, Gd, Dy, Er, Yb, Lu, Sm; the reflective layer 4 has a composition of REVO4、RETaO4、Y2O3One or more of RE, Y, Nd, Eu, Gd, Dy, Er, Yb, Lu and Sm. The component of the catadioptric layer 5 is one or a mixture of two of graphene and boron carbide, and the spatial distribution of the graphene and the boron carbide is in a disordered arrangement state; the insulating layer 6 is made of one or a mixture of epoxy resin, phenolic resin and ABS resin.
The invention utilizes ZrO2-RETaO4As the ceramic B layer, the ceramic B layer has the effects of low thermal conductivity and high expansion rate, and can reduce the heat conduction; and ZrO prepared by the following method2-RETaO4Can meet the requirements of APS spraying technology.
ZrO2-RETaO4The preparation method comprises the following steps:
step (1):
zirconium oxide (ZrO)2) Powder, rare earth oxide powder (RE)2O3) Tantalum pentoxide (Ta)2O5) Pre-drying the powder at 600 ℃ for 8 h; and in a molar ratio of 2 x: (1-x): (1-x) weighing zirconium oxide (ZrO)2) Powder, rare earth oxide powder RE2O3Tantalum oxide (Ta)2O5) Adding the powder into an ethanol solvent to obtain a mixed solution, wherein the molar ratio of RE to Ta to Zr in the mixed solution is (1-x) to 2 x; and then ball milling is carried out on the mixed solution for 10 hours by adopting a ball mill, and the rotating speed of the ball mill is 300 r/min.
Drying the slurry obtained after ball milling by using a rotary evaporator (model: N-1200B), wherein the drying temperature is 60 ℃, the drying time is 2h, and sieving the dried powder by using a 300-mesh sieve to obtain powder A.
Step (2):
preparing ZrO from the powder A obtained in the step (1) by adopting a high-temperature solid-phase reaction method2Doped RETaO4The reaction temperature of the powder B is 1700 ℃, and the reaction time is 10 hours; and the powder B was sieved using a 300 mesh sieve.
And (3):
mixing the powder B sieved in the step (2) with a deionized water solvent and an organic adhesive to obtain slurry C, wherein the mass percent of the powder B in the slurry C is 25%, the mass percent of the organic adhesive is 2%, and the balance is the solvent, and the organic adhesive is polyvinyl alcohol or gum arabic; drying the slurry C by using a centrifugal atomization method at the temperature of 600 ℃ at the centrifugal speed of 8500r/min to obtain dried granules D;
and (4):
sintering the material particles D obtained in the step (3) at 1200 ℃ for 8h, and sieving the sintered material particles D by using a 300-mesh sieve to obtain spherical ZrO with particle size of 10-70 nm2-RETaO4Ceramic powder.
The inventor finds out through a large number of experiments that the service temperature of the prepared ultra-limit aluminum alloy is increased most and the weight increase of the aluminum alloy is small within the parameter range of the invention, and 30 groups of the aluminum alloy are listed for illustration in the invention.
The parameters of examples 1 to 30 of an ultra-limited aluminum alloy and a method for producing the same according to the present invention are shown in tables 1, 2 and 3: (thickness unit: μm)
TABLE 1
Figure BDA0001931074610000071
Figure BDA0001931074610000081
Figure BDA0001931074610000091
TABLE 2
Figure BDA0001931074610000092
Figure BDA0001931074610000101
Figure BDA0001931074610000111
Figure BDA0001931074610000121
TABLE 3
Figure BDA0001931074610000122
Figure BDA0001931074610000131
Figure BDA0001931074610000141
Now, taking example 1 as an example, a method for preparing an ultra-limit aluminum alloy according to another embodiment of the present invention will be described.
A preparation method of an ultra-limit aluminum alloy comprises the following steps:
the method comprises the following steps:
in this example, 7072 aluminum alloy was selected as the aluminum alloy substrate, and oil stains and impurities on the surface of the aluminum alloy substrate were removed by a soaking method, and the aluminum alloy substrate was first soaked in an emulsion cleaning solution or an alkali solution, wherein the emulsion cleaning solution mainly contains ethanol and a surfactant, and the alkali solution mainly contains sodium hydroxide, trisodium phosphate, and sodium carbonate-sodium silicate, and the aluminum alloy substrate was soaked in the alkali solution in this example. Adjusting the pH value of the alkali solution to 10-11, soaking the aluminum alloy substrate in the alkali solution for 0.5-1.5h, taking out the aluminum alloy substrate, wherein the soaking time is 1h in the embodiment, and then washing the aluminum alloy substrate by using clear water and drying the aluminum alloy substrate. Shot blasting is carried out on the surface of the aluminum alloy substrate by using a shot blasting machine, the used shot blasting machine is a JCK-SS500-6A automatic transmission type shot blasting machine, the shot blasting material adopted in shot blasting is any one of iron sand, glass shot and ceramic shot, the iron sand is used in the embodiment, the particle size of the iron sand is 0.3-0.8mm, and the particle size of the iron sand is 0.5mm in the embodiment; the surface roughness of the aluminum alloy matrix after shot blasting is 60-100 μm, and the surface roughness of the aluminum alloy matrix in the embodiment is 80 μm, so that the coating and the aluminum alloy matrix are convenient to bond.
Step two:
a composite bonding layer is deposited on the surface of 7072 aluminum alloy after shot blasting, firstly, a NiCrCoAlY layer is sprayed on the surface of an aluminum alloy substrate by using an HVOF or supersonic electric arc spraying method to be used as the bonding layer, and the powder particle size is 25-65 mu m, the oxygen flow is 2000SCFH, the kerosene flow is 18.17LPH, the carrier gas is 12.2SCFH, the powder feeding amount is 5RPM, the length of a gun barrel is 5in, and the spraying distance is 254mm when the powder is sprayed by using the HVOF method.
And depositing a layer of Au as a noble metal layer on the NiCrCoAlY by using an EB-PVD method so as to form the composite bonding layer. The gas pressure during Au deposition is less than 0.01Pa, the pressure used in the embodiment is 0.008Pa, and the ratio of the temperature of the aluminum alloy substrate to the melting point of the aluminum alloy substrate is less than 0.3. The thickness of the deposited bonding layer was 50 μm and the thickness of the noble metal layer was 50 μm.
Step three:
spraying a layer of YSZ on the surface of the bonding layer as a ceramic A layer by APS, HVOF, PS-PVD or EB-PVD, wherein APS is used in the embodiment, and a layer of ZrO is sprayed on the ceramic A layer by APS2-YTaO4Forming a composite ceramic layer as a ceramic layer B; wherein the thickness of the ceramic A layer is 70 μm and the thickness of the ceramic B layer is 80 μm.
Step four:
ceramics prepared by HVOF, PS-PVD or EB-PVD methodSpraying a layer of Y on the surface of the porcelain B layer2O3The transparent ceramic material was used as a reflective layer, and the thickness of the reflective layer sprayed was 10 μm in this example using the HVOF method.
Step five:
uniformly mixing graphene and micron-sized carbon powder materials, introducing the mixed powder into a solution for ultrasonic vibration mixing, wherein the solution is an ethanol solution added with 1% of a dispersing agent, and separating the micron-sized carbon powder from the uniformly mixed solution by using filter paper. And coating the solution mixed with the graphene on the surface of the reflecting layer to serve as a catadioptric layer, putting the aluminum alloy coated with the graphene catadioptric layer into a drying oven, and drying at 60 ℃ for 2 hours, wherein the thickness of the coated catadioptric layer is 10 micrometers.
Step six:
and coating a layer of epoxy resin on the surface of the catadioptric layer to serve as an insulating layer, wherein the thickness of the insulating layer is 15 micrometers.
Step seven:
and coating a foam carbon layer on the insulating layer, wherein the thickness of the foam carbon layer is 20 mu m, and obtaining the ultra-limit aluminum alloy.
Examples 2-29 differed from example 1 only in the parameters shown in table 1; example 30 differs from example 1 in the spraying sequence of the ceramic a and B layers in step three.
Experiment:
set up 13 sets of comparative experiments with the comparative examples 1-30, the parameters of comparative examples 1-12 are shown in table 4:
TABLE 4
Figure BDA0001931074610000161
Figure BDA0001931074610000171
Comparative examples 1 to 12 differ from example 1 only in the respective parameters shown in table 3, and comparative example 13 is 7072 aluminum alloy.
The following experiments were carried out using the aluminum alloys provided in examples 1 to 30 and comparative examples 1 to 13:
high temperature creep test:
the aluminum alloys provided in examples 1 to 30 and comparative examples 1 to 13 were processed into columnar test pieces 187mm in length and 16mm in diameter, and high-temperature creep tests were conducted using an electronic high-temperature creep rupture strength tester of model RMT-D5.
The test pieces of examples 1 to 30 and comparative examples 1 to 13 were placed in an electronic high-temperature creep rupture strength tester, and the tester was started to raise the temperature of the tester, and during the temperature raising, the test pieces were in an unstressed state (in the unstressed state, the test pieces were free to expand, and the high-temperature creep was deformed by the combined action of temperature and stress and increased with time, so that the rate of temperature rise did not affect the creep). When the temperature of the testing machine reached 900 ℃, the testing machine was adjusted to a stress of 50MPa, and a high temperature creep test was conducted, taking example 1 and comparative example 13 as examples, the test results are shown in fig. 2 (a) shows comparative example 13, (B) shows example 1), and the specific test results of examples 1 to 30 and comparative examples 1 to 13 are shown in table 5.
As can be seen from fig. 2, the (a) and (B) test pieces had 3 stages of creep, but at temperatures above the melting point of the 7072 aluminum alloy, the (a) test piece had creep rupture in a very short time, and it can be seen that the 7072 aluminum alloy was hardly loaded at temperatures above the melting point of the 7072 aluminum alloy. Compared with the test piece (A), the creep resistance of the test piece (B) is obviously improved, the steady-state creep time of the test piece (B) is longer, and the creep curve enters an accelerated creep stage and generates creep fracture after passing through a longer steady-state creep stage. Therefore, compared with the original 7072 aluminum alloy, the ultra-limit aluminum alloy provided by the invention has the advantages that the ultra-limit aluminum alloy maintains better mechanical property without cracking and has excellent high-temperature resistance at the temperature exceeding the melting point of the 7072 aluminum alloy.
Salt spray corrosion test:
the aluminum alloys provided in examples 1 to 30 and comparative examples 1 to 13 were processed into 50mm × 25mm × 2mm test pieces, and then subjected to oil removal and rust removal treatment, cleaning, and drying. An YWX/Q-250B salt spray corrosion box is used as experimental equipment, and an atmospheric corrosion environment of GB/T2967.3-2008 is simulated.
The test pieces provided in examples 1 to 30 and comparative examples 1 to 13 were hung in an experimental apparatus, the temperature of the experimental apparatus was adjusted to 50. + -. 1 ℃ and pH was adjusted to 3.0 to 3.1, and NaCl solution having a concentration of 5. + -. 0.5% was continuously sprayed to the test pieces. Taking example 1 and comparative example 13 as examples, after spraying NaCl solution with concentration of 5 +/-0.5% for 8h, 24h, 48h and 72h continuously to the test piece, the weight loss rate of the test piece is shown in FIG. 3 (A) represents comparative example 13, (B) represents example 1), and the specific experimental results of examples 1-30 and comparative examples 1-13 are shown in Table 5.
It can be found by combining fig. 3 that the (a) and (B) test pieces have obviously different corrosion rules, and the corrosion weight loss value of the (a) test piece (7072 aluminum alloy) tends to increase with the increase of the corrosion time. In the initial stage of corrosion (8-24h), an oxide film exists on the surface of the sample, so that the contact between an aluminum alloy matrix and a solution is prevented, and the corrosion rate is low. In the middle stage of corrosion (24-48h), Cl-in the solution penetrates through the oxide film, and a large amount of Cl-is adsorbed on the substrate, so that the pitting pits are increased, the original pitting pits are deepened, and the corrosion rate is obviously accelerated. After the continuous spraying is carried out for 48 hours, the corrosion products are uniformly distributed, the thickness is increased, the corrosion products almost cover the whole surface of the sample, Cl < - > can contact with the aluminum alloy substrate only after penetrating through the corrosion products, the amount of Cl < - > adsorbed on the surface of the substrate is reduced, and the corrosion rate is reduced. In general, (A) the corrosion weight loss of the test piece is far higher than that of the test piece (B), and the quality of the test piece (B) is hardly changed because the coating is basically not corroded, so that the ultra-limit aluminum alloy provided by the application has better corrosion resistance.
The results of the experiment are shown in table 5: (A, stable creep time (min) of each test piece at 50MPa and 900 ℃, creep rupture time (min) of each test piece at B, 50MPa and 900 ℃, and C, weight loss rate (v/mg. cm) of each test piece after NaCl solution is continuously sprayed on the test pieces for 8 hours2) (ii) a D. And (3) continuously spraying NaCl solution to the test piece for 24 hours to obtain the weight loss ratio (v/mg2) (ii) a G. And (3) continuously spraying NaCl solution to the test piece for 48 hours to obtain the weight loss ratio (v/mg2) (ii) a E. And (3) continuously spraying NaCl solution to the test piece for 72 hours to obtain the weight loss ratio (v/mg2))
TABLE 5
Figure BDA0001931074610000191
Therefore, the composite bonding layer, the composite ceramic layer, the reflecting layer, the catadioptric layer, the insulating layer and the foam carbon layer are deposited on the aluminum alloy, so that the service temperature of the aluminum alloy can be increased to be higher than 100-fold-500 ℃ of the original melting point, and the corrosion resistance is greatly improved. And the thickness of each coating is controlled within the range provided by the invention, so that each effect of the prepared ultra-limit aluminum alloy can be optimal. The maximum service temperature of the aluminum alloy beyond the parameter range provided by the embodiment is much lower than that of the ultra-limit aluminum alloy provided by the invention, and the corrosion resistance of the aluminum alloy is poor.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and these changes and modifications should not be construed as affecting the performance of the invention and its practical application.

Claims (4)

1. An ultra-limit aluminum alloy comprises an aluminum alloy matrix and is characterized in that: the composite bonding layer and the composite ceramic layer are sequentially deposited on the surface of the aluminum alloy substrate; the composite bonding layer comprises a bonding layer deposited on the surface of the aluminum alloy substrate and a noble metal layer deposited on the surface of the bonding layer; the composite ceramic layer comprises a ceramic layer A and a ceramic layer B; the thickness of the composite bonding layer is 100-200 mu m, the thickness of the composite ceramic layer is 150-500 mu m, and a reflecting layer with the thickness of 10-30 mu m, a catadioptric layer with the thickness of 10-30 mu m, an insulating layer with the thickness of 10-200 mu m and a foam carbon layer with the thickness of 20-200 mu m are sequentially deposited outside the composite ceramic layer; the bonding layer is made of one or a mixture of more of MCrAlY, NiAl, NiCr-Al and Mo, and the MCrAlY is NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY; the component of the noble metal layer is one of Au, Pt, Ru, Rh, Pd and IrOr an alloy of several; the ceramic layer A contains YSZ or rare earth zirconate (RE)2Zr2O7) (ii) a The component of the ceramic B layer is ZrO2-RETaO4(ii) a The composition of the reflecting layer is REVO4、RETaO4、Y2O3One or a mixture of several of them; the component of the catadioptric layer is one or a mixture of two of graphene or boron carbide, and the spatial distribution of the graphene and the boron carbide is in a disordered arrangement state; the insulating layer is composed of one or a mixture of more of epoxy resin, phenolic resin and ABS resin.
2. An ultra-limited aluminum alloy as set forth in claim 1, wherein: the ZrO2-RETaO4Is spherical and has a particle size of 10-70 μm.
3. A method for producing an ultra-limited aluminium alloy according to claim 1 or 2, comprising the steps of:
the method comprises the following steps:
firstly, depositing a bonding layer on the surface of an aluminum alloy substrate by using an HVOF or supersonic electric arc spraying method, and then depositing a noble metal layer on the surface of the bonding layer by using an EB-PVD method to form a composite bonding layer by using the bonding layer and the noble metal layer, wherein the total thickness of the composite bonding layer is 100-200 mu m;
step two:
depositing a ceramic layer A and a ceramic layer B on the surface of the noble metal layer by using an APS (advanced passivation solution), HVOF (high voltage oxygen gas), PS-PVD (PS-physical vapor deposition) or EB-PVD (electron beam physical vapor deposition) method, so that the ceramic layer A and the ceramic layer B form a composite ceramic layer, wherein the total thickness of the composite ceramic layer is 150-500 mu m;
step three:
depositing a reflecting layer on the surface of the composite ceramic layer by using an HVOF, PS-PVD or EB-PVD method, wherein the thickness of the reflecting layer is 10-30 mu m;
step four:
coating a catadioptric layer on the surface of the reflecting layer by a coating method, wherein the thickness of the catadioptric layer is 10-30 mu m;
step five:
coating an insulating layer on the surface of the catadioptric layer by a coating method, wherein the thickness of the insulating layer is 10-200 mu m;
step six:
and (3) coating a foamed carbon layer on the surface of the insulating layer by using a coating method, wherein the thickness of the foamed carbon layer is 20-200 mu m, so that the ultra-limit aluminum alloy is formed.
4. The method for preparing the ultra-limit aluminum alloy as recited in claim 3, wherein: in the first step, before the bonding layer is deposited, oil stains on the surface of the aluminum alloy substrate are removed; and shot blasting the surface of the aluminum alloy matrix to ensure that the surface roughness of the aluminum alloy matrix is 60-100 mu m.
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