CN109554708B - Ultra-limit titanium alloy and preparation method thereof - Google Patents

Ultra-limit titanium alloy and preparation method thereof Download PDF

Info

Publication number
CN109554708B
CN109554708B CN201811645669.0A CN201811645669A CN109554708B CN 109554708 B CN109554708 B CN 109554708B CN 201811645669 A CN201811645669 A CN 201811645669A CN 109554708 B CN109554708 B CN 109554708B
Authority
CN
China
Prior art keywords
layer
titanium alloy
thickness
ceramic
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811645669.0A
Other languages
Chinese (zh)
Other versions
CN109554708A (en
Inventor
冯晶
杨凯龙
宋鹏
种晓宇
葛振华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201811645669.0A priority Critical patent/CN109554708B/en
Publication of CN109554708A publication Critical patent/CN109554708A/en
Priority to EP19903063.6A priority patent/EP3904555A4/en
Priority to JP2021538453A priority patent/JP7242867B2/en
Priority to PCT/CN2019/117283 priority patent/WO2020134655A1/en
Priority to US17/419,250 priority patent/US11530485B2/en
Application granted granted Critical
Publication of CN109554708B publication Critical patent/CN109554708B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B05D5/063—Reflective effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
    • B05D2202/35—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) based on Ti

Abstract

The invention belongs to the technical field of titanium alloy materials, and discloses an ultra-limit titanium alloy and a preparation method thereof, wherein the ultra-limit titanium alloy comprises a titanium alloy substrate, and 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 titanium alloy substrate; the composite bonding layer comprises a bonding layer deposited on the surface of the titanium 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. According to the invention, the multilayer coating is deposited on the surface of the titanium alloy substrate, so that the use temperature of the titanium alloy substrate can be raised to be higher than the melting point of the original titanium alloy substrate by 100-. The ultra-limit titanium 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 the titanium alloy matrix, and increases the application range.

Description

Ultra-limit titanium alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of titanium alloy material preparation, and particularly relates to an ultra-limit titanium alloy and a preparation method thereof.
Background
The titanium alloy has the characteristics of high strength, small specific gravity, good corrosion resistance, high heat resistance, high hardness, good biocompatibility and the like, the titanium-based alloy is widely applied to the fields of aviation, aerospace, submarines, medical treatment and the like in the 20 th century, the first practical titanium alloy is a Ti-6Al-4V alloy which is successfully developed in the United states in 1954, and then becomes a King brand alloy in the titanium alloy industry, and the usage amount of the alloy accounts for 75-85% of the total titanium alloy. Many other titanium alloys can be considered as modifications of the Ti-6Al-4V alloy. The titanium alloy can still maintain the mechanical property at low temperature and ultralow temperature. Titanium alloys with good low temperature properties and extremely low interstitial elements, such as TA7, can maintain certain plasticity at-253 ℃. Titanium alloy is a new important structural material used in the aerospace industry, such as an American SR-71 high-altitude high-speed scout aircraft (the flight Mach number is 3, the flight height is 26212 meters), and titanium accounts for 93 percent of the structural weight of the aircraft, so that the aircraft is called an all-titanium aircraft.
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 running speed of an engine is gradually increased, so that the surface temperature of an engine blade is gradually increased, although the titanium alloy has a plurality of excellent performances, because the limit service temperature of the titanium alloy is only 400-500 ℃, with the increasing requirement of an aircraft engine with a high thrust-weight ratio, the performance of various high-temperature component materials is also strictly required, and in addition, when the metal works at a temperature of more than half of the melting point of the metal, the phenomenon of softening occurs, namely when the titanium alloy works at an environment of about 540 ℃, the phenomenon of softening occurs and the performance is reduced, namely, the current titanium alloy cannot be used at a temperature exceeding the limit (exceeding the melting point temperature of the titanium alloy).
Generally, it is considered that when one material cannot be used in a high-temperature environment, another material with a higher melting point is sought, for example, it is generally considered that a nickel alloy, an iron alloy and the like with a higher melting point can replace a titanium alloy to work at a higher temperature, but the atomic weight of the alloy is large, so that the material with the same thickness is obtained, the nickel alloy or the iron alloy is heavier, so that the alloy can meet the requirement of high temperature but cannot achieve the effect of light weight, and the speed of an aircraft such as an aircraft is increased, which is the key to the weight of the aircraft, so that the speed increase of the aircraft such as the aircraft presents a bottleneck. Therefore, 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 a super-limit titanium alloy and a preparation method thereof, and aims to solve the problem that the existing titanium alloy cannot be used at a super-limit temperature.
To achieve the above object, the present invention provides the following basic solutions:
the ultra-limit titanium alloy comprises a titanium alloy substrate, wherein a composite bonding layer and a composite ceramic layer are sequentially deposited on the surface of the titanium alloy substrate; the composite bonding layer comprises a bonding layer deposited on the surface of the titanium 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 extensive research, the inventor develops an ultra-limit titanium alloy which meets the requirement that the titanium alloy is used at an ultra-limit temperature (exceeding the melting point 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 other high-melting-point alloys are required to be used, and the inventor does not go so far and tries to improve the titanium 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 titanium alloy can be increased to be higher than the original melting point by 100-500 ℃ by depositing a coating with a certain proportion on the surface of the titanium alloy, so that the use temperature of the titanium alloy can be greatly increased, and the requirement of manufacturing an aircraft can be met; in a high-temperature environment, the use temperature of the titanium 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 titanium alloy.
According to the technical scheme, the composite bonding layer and the composite ceramic layer are deposited on the titanium alloy substrate, so that the service temperature of the titanium alloy can be greatly increased, and the titanium alloy is suitable for being used under the condition of exceeding the limit temperature. The composite bonding layer is deposited, so that the bonding effect between each coating and the titanium 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 titanium alloy matrix can be increased. According to the technical scheme, the service temperature of the titanium alloy is greatly improved through the matching of the coatings.
In summary, the present invention has the following technical effects:
1. the ultra-limit titanium 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 the titanium alloy matrix, and increases the application range.
2. According to the invention, the multilayer coating is deposited on the surface of the titanium alloy substrate, so that the use temperature of the titanium alloy substrate can be raised to be higher than the melting point of the original titanium alloy substrate by 100-.
3. The ultra-limit titanium alloy provided by the invention has excellent corrosion resistance, so that the service time under acidic or alkaline conditions is greatly increased, 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 titanium alloy can be applied to the preparation of the engine blade of the aircraft, the use requirement of the engine temperature rise when the aircraft speeds up can be met, and the speed of the aircraft is increased.
Furthermore, the thickness of the bonding layer is 20-30 μm, the thickness of the noble metal layer is 40-60 μm, the thickness of the composite ceramic layer is 100-150 μm, and a reflecting layer with the thickness of 10-30 μm, a catadioptric layer with the thickness of 20-30 μm, an insulating layer with the thickness of 100-200 μm and a foam carbon layer with the thickness of 20-200 μm are sequentially deposited on the composite ceramic layer.
Has the advantages that: the reflecting layer has the effect of reflecting heat sources, so that the heat sources on the surface of the titanium alloy are reduced, and the service temperature is increased. The deposited catadioptric layer can block the refraction of infrared rays in the coating, so that the temperature of the titanium alloy matrix is reduced, and the service temperature of the prepared titanium alloy is increased. The effect of depositing the insulating layer is that the surface of the material is easy to ionize in the ultra-high speed environment, and the insulating layer can prevent conductive ions or electrons generated by ionization from entering the titanium alloy matrix, so that the corrosion of charges to the titanium alloy matrix is resisted. 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 titanium alloy substrate, so that the heat transmission is further prevented, and the use temperature of the titanium alloy is increased. And the thickness of each coating is set, so that the service temperature of the prepared ultra-limit titanium alloy can be increased, the heat insulation effect of the coatings is ensured, the weight of the coatings is also controlled, and the aircraft can be conveniently used.
Furthermore, the bonding layer is one or a mixture of more of MCrAlY, NiAl, NiCr-Al and Mo alloy, and 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: in the three materials of NiCrCoAlY, NiCoCrAlY and CoNiCrAlY, the content of each element is reduced in turn according to the chemical formula, and the proportion of each element is different, so that the prepared materials are different. The bonding layer has good bonding effect, so that the subsequent coating and the titanium 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 titanium 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) The component of the ceramic B layer is ZrO2-RETaO4。
Has the advantages that: YSZ or rare earth zirconate is the most commonly used component of the ceramic layer in the current thermal barrier coating, and the preparation process is mature and convenient to purchase; and ZrO2-RETaO4The titanium alloy has the effects of high expansion coefficient and low thermal conductivity, wherein the low thermal conductivity can reduce the conduction of external heat into the titanium alloy matrix, so that the titanium alloy matrix can keep a lower temperature in a high-temperature environment; for the high expansion coefficient, the coating is used as a whole and does not act singly, the high expansion coefficient is matched with the thermal expansion coefficient of the bonding layer, and the thermal mismatch stress (stress generated by different thermal expansion coefficients) of the ceramic layer and the bonding layer is small in the thermal cycle process (namely the process of continuously heating and cooling) because the thermal expansion coefficient of the noble metal bonding layer is large, so that the service life of the coating is 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 reflective layer has a composition of REVO4、RETaO4、Y2O3One or a mixture of several of them.
Has the advantages that: the reflection coefficients of REVO4, RETaO4 and Y2O3 are high, so that the reflection effect on heat radiation is good, the temperature of a titanium alloy matrix in a high-temperature environment is greatly reduced, and the service temperature of the prepared titanium alloy is improved.
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: because the spatial distribution of graphite alkene or boron carbide is the state of unordered range, though graphite alkene or boron carbide have higher refracting index, when the infrared light when shining on graphite alkene catadioptric layer, the graphite alkene of unordered range can strengthen the refraction of light in all directions, avoids incident light to take place the refraction in same direction, reaches the effect that the refraction is dispersed, enters into the intensity decline of the infrared light in the coating like this to reduce the temperature of coating and titanium alloy base member.
Further, the insulating layer is made of one or a mixture of epoxy resin, phenolic resin and ABS resin.
Has the advantages that: taking an aircraft as an example, in the process of high-speed flight, the outer surface of the aircraft rubs with air, so that the air is ionized to form conductive ions or electrons, and the inventor verifies through experiments that the adoption of organic coatings such as epoxy resin and phenolic resin can effectively resist the electric charges entering the coatings and the titanium alloy matrix, thereby reducing the corrosion of the conductive electrons or ions to tin alloy welding seams.
The invention also provides another technical scheme, and the preparation method of the ultra-limit titanium alloy comprises the following steps:
step 1: depositing a bonding layer on the surface of the titanium alloy substrate; depositing a noble metal layer on the surface of the bonding layer to form a composite bonding layer by the bonding layer and the noble metal layer, wherein the total thickness of the composite bonding layer is 60-90 mu m;
step 2: depositing a ceramic layer A and a ceramic layer B on the surface of the composite bonding layer obtained in the step 1 to form a composite ceramic layer, wherein the total thickness of the composite ceramic layer is 100-150 mu m;
and step 3: depositing a reflecting layer on the surface of the composite ceramic layer obtained in the step 2, wherein the thickness of the reflecting layer is 10-30 mu m;
and 4, step 4: depositing a catadioptric layer on the surface of the reflecting layer obtained in the step (3), wherein the thickness of the catadioptric layer is 20-30 mu m;
and 5: depositing an insulating layer on the surface of the catadioptric layer obtained in the step 4, wherein the thickness of the insulating layer is 100-200 mu m;
step 6: and (5) depositing a foam carbon layer on the surface of the insulating layer obtained in the step 5, wherein the thickness of the foam carbon layer is 20-200 mu m, so that the ultra-limit titanium alloy is formed.
The beneficial effects of the technical scheme are as follows:
by controlling the thickness of each coating deposited on the titanium alloy substrate, the service temperature of the prepared ultra-limit titanium alloy can be increased to 100-500 ℃ higher than the melting point of the original titanium alloy, and the titanium alloy has excellent corrosion resistance. Meanwhile, the situation that the weight of the prepared ultra-limit titanium alloy is increased greatly due to the fact that the thickness of the coating is large can be avoided, and therefore the ultra-limit titanium alloy can meet the use requirement of an aircraft.
Further, in the step 2, ZrO is formed to form the ceramic B layer2-RETaO4Is powder, the ZrO2-RETaO4The particle size of the powder is 10-70 mu m, and the shape of the powder is spherical.
Has the advantages that: ZrO with particle size of 10-70 mu m and spherical shape is adopted2-RETaO4The coating prepared from the powder is spherical, so that the surface of the powder is smooth, the powder has good fluidity, and a high-quality ceramic coating is obtained.
Further, in the step 1, before depositing the bonding layer, the surface of the titanium alloy substrate is pretreated, wherein the pretreatment comprises degreasing and impurity removal; after the surface of the titanium alloy matrix is pretreated, shot blasting is carried out on the surface of the titanium alloy matrix, so that the surface roughness of the titanium alloy matrix is 60-100 mu m.
Has the advantages that: before the bonding layer is deposited, the surface of the titanium alloy substrate is subjected to degreasing and impurity removal treatment, so that oil stains and impurities can be prevented from entering the coating, the quality of the coating is influenced, and the problem that the coating is cracked or even falls off is avoided; the surface roughness of the titanium alloy substrate can be improved by performing shot blasting treatment on the surface of the titanium alloy substrate, so that the bonding strength between the surface of the titanium alloy substrate and the bonding layer is improved, and the probability of falling off of the bonding layer is reduced.
Drawings
FIG. 1 is a schematic structural view of a super-limit titanium alloy according to the present invention;
FIG. 2 is a graph showing the high temperature creep test of example 1 and comparative example 13 under a stress of 50MPa and at a temperature of 1900 ℃;
FIG. 3 is a graph of salt spray corrosion experiments for example 1 and comparative example 13 of the present invention.
Detailed Description
The following is further detailed by way of specific embodiments:
reference numerals in the drawings of the specification include: the titanium alloy light-emitting diode comprises a titanium alloy substrate 1, a bonding layer 2, a noble metal layer 3, a ceramic A layer 4, a ceramic B layer 5, a reflecting layer 6, a catadioptric layer 7, an insulating layer 8 and a foam carbon layer 9.
The invention provides a super-limit titanium alloy, which comprises a titanium alloy substrate 1, wherein a composite bonding layer, a composite ceramic layer with the thickness of 100-150 mu m, a reflecting layer 6 with the thickness of 10-30 mu m, a catadioptric layer 7 with the thickness of 20-30 mu m, an insulating layer 8 with the thickness of 100-200 mu m and a foam carbon layer 9 with the thickness of 20-200 mu m are sequentially deposited on the surface of the titanium alloy substrate 1 as shown in figure 1. The composite bonding layer is a bonding layer 2 deposited on the surface of a titanium alloy substrate 1 and a precious metal layer 3 deposited on the surface of the bonding layer 2, the thickness of the bonding layer 2 is 20-30 mu m, the thickness of the precious metal layer is 40-60 mu m, the bonding layer 2 is made of one or a mixture of more of MCrAlY, NiAl, NiCr-Al and Mo alloy, and the MCrAlY is NiCrCoAlY, NiCoCrAlY, CoNiCrAlY or CoCrAlY; the component of the noble metal layer 3 is one or more of Au, Pt, Ru, Rh, Pd and Ir; the composite ceramic layer comprises a ceramic A layer 4 and a ceramic B layer 5 which are deposited on the ceramic A layerThe porcelain A layer 4 is composed of YSZ or rare earth zirconate (RE)2Zr2O7RE ═ Y, Gd, Nd, Sm, Eu, or Dy), the component of the ceramic B layer 5 is ZrO2-RETaO4(RE ═ Y, Gd, Nd, Sm, Eu, Dy, Er, Yb, Lu); the reflecting layer 6 is REVO4、RETaO4、Y2O3One or more of RE, Y, Nd, Sm, Eu, Gd, Dy, Er, Yb and Lu. The component of the catadioptric layer 7 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 8 is made of one or a mixture of epoxy resin, phenolic resin and ABS resin.
Wherein ZrO2-RETaO4The powder is prepared by the following method, which comprises the following steps:
step (1): ZrO 2 is mixed with2Powder, rare earth oxide (RE)2O3) Powder, tantalum pentoxide (Ta)2O5) Pre-drying the powder at 600 ℃ for 8 h; according to ZrO2-RETaO4The dried ZrO was weighed in a molar ratio of2Powder, rare earth oxide (RE)2O3) Powder, tantalum pentoxide (Ta)2O5) Powder; adding the pre-dried 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 1:1: 1; 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 method2-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 ZrO with particle size of 10-70 mu m and spherical appearance2-RETaO4Ceramic powder.
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 above method2-RETaO4Can meet the requirements of APS spraying technology on the particle size and the shape of the powder.
The inventor finds out through a large number of experiments that the service temperature of the prepared ultra-limit titanium alloy is increased to the maximum within the parameter range of the invention, the weight increase of the titanium alloy is small, and the ultra-limit titanium alloy with the optimal coating composition and thickness is provided, and 30 groups are listed for description in the invention.
The parameters of examples 1 to 30 of the ultra-limiting titanium alloy and the preparation method thereof of the present invention are shown in tables 1, 2 and 3:
TABLE 1 composition and thickness of each coating layer in examples 1-10 of an ultra-limiting titanium alloy and a method for preparing the same
Figure BDA0001932008830000071
Figure BDA0001932008830000081
Figure BDA0001932008830000091
TABLE 2 composition and thickness of each coating layer in examples 11 to 20 of an ultra-limiting titanium alloy and a method for preparing the same
Figure BDA0001932008830000102
Figure BDA0001932008830000111
Figure BDA0001932008830000121
TABLE 3 composition and thickness of each coating layer in examples 21 to 30 of an ultra-limiting titanium alloy and a method for preparing the same
Figure BDA0001932008830000122
Figure BDA0001932008830000131
Figure BDA0001932008830000151
Now, a method for preparing a super-limit titanium alloy according to another embodiment of the present invention will be described with reference to example 1.
A preparation method of an ultra-limit titanium alloy comprises the following steps:
step 1: the method includes the steps of removing oil stains and impurities on the surface of a titanium alloy matrix by using a soaking method, selecting TC4 titanium alloy as a material of the titanium alloy matrix in the embodiment, soaking the titanium alloy matrix for 0.5-1.5 hours by using a solvent or an alkali solution, wherein the main components of the solvent are ethanol and a surfactant, the main components of the alkali solution are sodium hydroxide, trisodium phosphate, sodium carbonate, sodium silicate and the like, the pH value of the alkali solution is 10-11, cleaning the surface of the titanium alloy matrix by using the solvent in the embodiment, taking out the titanium alloy matrix after the oil stains and the impurities are cleaned, washing the titanium alloy matrix by using deionized water, and drying the titanium alloy matrix.
Shot blasting is carried out on the surface of the titanium 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 titanium alloy matrix after shot blasting is 60-100 μm, and the surface roughness of the titanium alloy matrix in the embodiment is 80 μm, so that the coating and the titanium alloy matrix can be conveniently bonded.
Step 2: depositing a composite bonding layer on the surface of the titanium alloy matrix after shot blasting, firstly spraying a NiCrCoAlY layer on the surface of the titanium alloy matrix by using an HVOF method (supersonic flame spraying method) or a supersonic electric arc spraying method as the bonding layer, wherein the HVOF method is used in the embodiment, and the HVOF method has the process parameters as follows: the powder particle diameter was 25-65 μm, the oxygen flow rate was 2000SCFH, the kerosene flow rate was 18.17LPH, the carrier gas was 12.2SCFH, the powder feed rate was 5RPM, the barrel length was 5in, and the spray distance was 254 mm.
And then, a layer of Au is deposited on the NiCrCoAlY bonding layer by using an EB-PVD method (an electron beam physical vapor deposition method) to serve as a noble metal layer, so that the composite bonding layer is formed. The gas pressure when depositing Au is less than 0.01Pa, and the technological parameters of the EB-PVD method are as follows: the pressure is 0.008Pa, the deposition rate is 6nm/min, and the ratio of the temperature of the titanium alloy substrate to the melting point of the titanium alloy substrate is less than 0.3. The thickness of the deposited tie layer was 20 μm and the thickness of the noble metal layer was 50 μm.
And step 3: spraying a layer of YSZ on the surface of the composite bonding layer as a ceramic A layer by APS (atmospheric plasma spraying), HVOF, PS-PVD or EB-PVD, wherein HVOF is used in the embodiment, and spraying a layer of ZrO on the YSZ ceramic A layer by HVOF2-YTaO4 as a ceramic B layer forming a composite ceramic layer; wherein the thickness of the ceramic layer A is 70 μm, and the ceramic layer A is made of ceramicThe thickness of the porcelain B layer was 80 μm.
And 4, step 4: spraying a layer of Y on the surface of the composite ceramic layer by using HVOF method2O3The transparent ceramic material is used as a reflecting layer, and the thickness of the sprayed reflecting layer is 10 mu m.
And 5: by applying a brush on Y2O3The surface of the reflecting layer is coated with a layer of graphene as a catadioptric layer, and the thickness of the catadioptric layer is 20 mu m.
The graphene has a high specific surface area and is extremely difficult to dissolve in a solution, so that the graphene needs to be subjected to ultrasonic dispersion and solid-liquid separation before coating, namely, the graphene and a micron-sized carbon powder material are uniformly mixed, then mixed powder is introduced into the solution to be subjected to ultrasonic vibration mixing, the solution in the embodiment is an ethanol solution added with 1% of a dispersing agent, the micron-sized carbon powder is separated from the uniformly mixed solution by using filter paper, finally the solution mixed with the graphene is coated on the surface of a reflecting layer, and then the titanium alloy coated with a graphene catadioptric layer is placed in a drying box and dried for 2 hours at the temperature of 60 ℃.
In addition, after the graphene is subjected to ultrasonic dispersion, the spatial distribution of the graphene is rearranged in all directions, so that the spatial distribution of the graphene is in a disordered arrangement state, the graphene has a higher refractive index, when incident light irradiates on a graphene catadioptric layer, the refraction of light in all directions can be enhanced by the disordered arranged graphene, the incident light is prevented from being refracted in the same direction, the effect of refraction dispersion is achieved, and the incident light intensity entering the coating is reduced.
Step 6: and (3) coating a layer of epoxy resin as an insulating layer on the surface of the graphene catadioptric layer by using a coating method, wherein the thickness of the insulating layer is 150 micrometers.
And 7: a carbon foam layer was coated on the epoxy resin insulation layer by a brushing method, and the carbon foam layer had a thickness of 20 μm.
Examples 2-29 were prepared in the same manner as example 1, except that the composition and thickness of each coating layer was different as shown in table 1; example 30 differs from example 1 in the spraying sequence of the ceramic a layer and the ceramic B layer in step 3.
In addition, 13 sets of comparative experiments were carried out on the comparative examples and examples 1 to 30.
Table 4 shows the composition and thickness of each coating of comparative examples 1-12:
Figure BDA0001932008830000171
Figure BDA0001932008830000181
comparative examples 1 to 12 were the same as in example 1 except that the composition and thickness of each coating layer were different as shown in table 3, and comparative example 13 was an un-deposited coating layer of TC4 titanium alloy substrate.
The following experiments were carried out using the titanium alloys provided in examples 1 to 30 and comparative examples 1 to 13:
1. high temperature creep test:
the titanium alloys prepared in examples 1 to 30 and comparative examples 1 to 13 were processed into tensile test pieces, and a high-temperature creep test was performed using an electronic high-temperature creep rupture strength tester of type RMT-D5, wherein the maximum test load was 50KN, the test load control accuracy was within. + -. 5%, the deformation measurement range was 0 to 10mm, and the rate adjustment range was 0 to 50mm/min-1The deformation resolution is 0.001mm, the temperature control range of the high-temperature furnace is 200-2000 ℃, and the length of the soaking zone is 150 mm.
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 test pieces were left in an unstressed state (in the unstressed state, the test pieces were free to expand, and high temperature creep is deformation that increases with time under the combined action of temperature and stress, so that the rate of temperature rise had no effect on creep). The tester was adjusted to a stress of 50MPa and a temperature of 1300 ℃, and the following data was recorded, as shown in table 5, wherein a in table 5 represents the steady creep time (min) of each test piece; b represents the time (min) for creep rupture of each test piece.
Taking example 1 and comparative example 13 as examples, as shown in fig. 2, which is a high temperature creep test graph of example 1 and comparative example 13, fig. 2 (a) shows the TC4 titanium alloy base material without depositing the coating in comparative example 13, and fig. 2 (B) shows the material prepared in example 1.
As can be seen from FIG. 2, there are 3 stages of (A) and (B) test piece creep at 1900 ℃ under a stress of 50 MPa: the first stage is short and has a large creep rate, and the first stage is quickly transited to a creep second stage, wherein the creep rate of the second stage reaches a minimum value, and the second stage is long and is basically in a steady-state creep process; in the third stage, the creep rate is rapidly increased, and creep deformation rapidly develops until the material is damaged and creep fracture occurs. Meanwhile, the test piece (A) can be found to be broken in a very short time under the stress of 50MPa and the temperature of 1900 ℃, which shows that the titanium alloy can hardly bear load under the temperature condition of higher than the melting point, while the test piece (B) can keep good mechanical property under the temperature of 1900 ℃ without breaking for a long time and has excellent high-temperature resistance.
2. Salt spray corrosion test:
the titanium alloys provided in examples 1 to 30 and comparative examples 1 to 13 were processed into test pieces of 50mm × 25mm × 2mm, and then subjected to oil removal and rust removal treatment, and then cleaned and dried. 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 a test apparatus, the temperature of the test apparatus was adjusted to 50 ± 1 ℃ and the PH was adjusted to 3.0 to 3.1, the test pieces were continuously sprayed with a NaCl solution having a concentration of 5 ± 0.5%, and the weight loss ratios of the respective test pieces were recorded in table 5 after a certain time (8, 24, 48, 72 hours). As shown in FIG. 3, the weight loss by salt spray corrosion is plotted against corrosion time for example 1 and comparative example 13, wherein (A) in FIG. 3 represents the TC4 titanium alloy base material of comparative example 13 without the deposited coating, and (B) in FIG. 3 represents the material prepared in example 1.
As can be seen from fig. 3, the two titanium alloys have significantly different corrosion laws, and the corrosion weight loss value of the (a) test piece (TC4 titanium alloy test piece) tends to increase with the increase of the corrosion time. Wherein, in the initial stage of corrosion (8-24h), an oxide film exists on the surface of the sample to prevent the titanium alloy matrix from reacting withThe corrosion rate is low when the solution is contacted. In the middle stage of corrosion (24-48h), Cl in the solution-(chloride ion) has penetrated the oxide film and a large amount of Cl-The corrosion inhibitor is adsorbed on a substrate, so that pitting pits are increased, original pitting pits are deepened, and the corrosion rate is obviously accelerated. After 48h of continuous spraying, the corrosion products were distributed uniformly and increased in thickness, covering almost the entire surface of the test specimen, with Cl-Needs to penetrate through corrosion products to be contacted with the titanium alloy substrate, and reduces the Cl adsorbed on the surface of the substrate-In such an amount that the corrosion rate is reduced. Overall, the TC4 titanium alloy has much higher corrosion weight loss than the titanium-based surface composite, which has little change in mass due to the substantial absence of corrosion caused by the presence of the coating.
In table 5, a represents the steady creep time (min) of each test piece; b represents the time (min) for creep rupture of each test piece;
c represents the weight loss rate (v/mg. cm2) of the test piece after the NaCl solution is continuously sprayed on the test piece for 8 hours;
d represents the weight loss rate (v/mg. cm2) of the test piece after the NaCl solution is continuously sprayed on the test piece for 24 hours;
e represents the weight loss rate (v/mg. cm2) of the test piece after the NaCl solution is continuously sprayed on the test piece for 48 hours;
f represents the weight loss rate (v/mg. cm2) of the test piece after the NaCl solution is continuously sprayed on the test piece for 72 hours.
Table 5 shows the results of the high temperature creep test and the salt spray test
Figure BDA0001932008830000211
As can be seen from table 5, the titanium alloy obtained in the comparative example, which is out of the parameter range of the present invention, has a greatly reduced stability at high temperature, is fractured in a short time, and has poor corrosion resistance.
In conclusion, the anti-oxidation 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 titanium alloy, so that the service temperature of the titanium alloy can be increased to 100-500 ℃ higher than the original melting point, and the corrosion resistance is greatly improved. The ultra-limit titanium alloy prepared by the preparation method of the ultra-limit titanium alloy provided by the invention has the advantages of wide use temperature range and strong corrosion resistance, wherein each effect of the embodiment 1 is the best.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.

Claims (4)

1. An ultra-limited titanium alloy comprising a titanium alloy matrix, characterized in that: a composite bonding layer and a composite ceramic layer are sequentially deposited on the surface of the titanium alloy substrate; the composite bonding layer comprises a bonding layer deposited on the surface of the titanium 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 bonding layer is 20-30 μm, the thickness of the noble metal layer is 40-60 μm, the thickness of the composite ceramic layer is 100-150 μm, and a reflecting layer with the thickness of 10-30 μm, a catadioptric layer with the thickness of 20-30 μm, an insulating layer with the thickness of 100-200 μm and a foam carbon layer with the thickness of 20-200 μm are sequentially deposited on the composite ceramic layer; the bonding layer is one or a mixture of more of MCrAlY, NiAl, NiCr-Al and Mo alloy, and 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; the ceramic layer A contains YSZ or rare earth zirconate (RE)2Zr2O7) 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; composition of catadioptric layerThe graphene or boron carbide is divided into 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 is composed of one or a mixture of more of epoxy resin, phenolic resin and ABS resin.
2. The method for preparing the ultra-limit titanium alloy according to claim 1, comprising the following steps:
step 1: depositing a bonding layer on the surface of the titanium alloy substrate by using an HVOF method; 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 thickness of the bonding layer is 20-30 mu m, and the thickness of the noble metal layer is 40-60 mu m;
step 2: depositing a ceramic layer A and a ceramic layer B on the surface of the composite bonding layer obtained in the step 1 by using an HVOF method, so that the ceramic layer A and the ceramic layer B form a composite ceramic layer, and the total thickness of the composite ceramic layer is 100-150 mu m;
and step 3: depositing a reflecting layer on the surface of the composite ceramic layer obtained in the step 2 by using an HVOF method, wherein the thickness of the reflecting layer is 10-30 mu m;
and 4, step 4: depositing a catadioptric layer on the surface of the reflecting layer obtained in the step (3) by using a painting method, wherein the thickness of the catadioptric layer is 20-30 mu m;
and 5: depositing an insulating layer on the surface of the catadioptric layer obtained in the step 4 by using a brushing method, wherein the thickness of the insulating layer is 100-200 mu m;
step 6: and (5) depositing a foam carbon layer on the surface of the insulating layer obtained in the step (5) by using a brushing method, wherein the thickness of the foam carbon layer is 20-200 mu m, so that the ultra-limit titanium alloy is formed.
3. The method for preparing the ultra-limit titanium alloy according to claim 2, wherein: in the step 2, ZrO of the ceramic B layer is formed2-RETaO4Is powder, the ZrO2-RETaO4The particle size of the powder is 10-70 mu m, and the shape of the powder is spherical.
4. The method for preparing the ultra-limit titanium alloy according to claim 3, wherein the method comprises the following steps: in the step 1, before depositing the bonding layer, the surface of the titanium alloy substrate is pretreated, wherein the pretreatment comprises degreasing and impurity removal; after the surface of the titanium alloy matrix is pretreated, shot blasting is carried out on the surface of the titanium alloy matrix, so that the surface roughness of the titanium alloy matrix is 60-100 mu m.
CN201811645669.0A 2018-12-29 2018-12-29 Ultra-limit titanium alloy and preparation method thereof Active CN109554708B (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201811645669.0A CN109554708B (en) 2018-12-29 2018-12-29 Ultra-limit titanium alloy and preparation method thereof
EP19903063.6A EP3904555A4 (en) 2018-12-29 2019-11-12 Ultralimit alloy and preparation method therefor
JP2021538453A JP7242867B2 (en) 2018-12-29 2019-11-12 Superalloy and its manufacturing method
PCT/CN2019/117283 WO2020134655A1 (en) 2018-12-29 2019-11-12 Ultralimit alloy and preparation method therefor
US17/419,250 US11530485B2 (en) 2018-12-29 2019-11-12 Ultralimit alloy and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811645669.0A CN109554708B (en) 2018-12-29 2018-12-29 Ultra-limit titanium alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109554708A CN109554708A (en) 2019-04-02
CN109554708B true CN109554708B (en) 2020-01-14

Family

ID=65872140

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811645669.0A Active CN109554708B (en) 2018-12-29 2018-12-29 Ultra-limit titanium alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109554708B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3904555A4 (en) 2018-12-29 2022-10-19 Kunming University Of Science And Technology Ultralimit alloy and preparation method therefor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9203394D0 (en) * 1992-02-18 1992-04-01 Johnson Matthey Plc Coated article
US20070138019A1 (en) * 2005-12-21 2007-06-21 United Technologies Corporation Platinum modified NiCoCrAlY bondcoat for thermal barrier coating
BRPI0712026A2 (en) * 2006-05-26 2012-01-03 Praxair Technology Inc blade for a gas turbine engine, and process for producing a lining on at least a portion of a blade tip for a gas turbine engine

Also Published As

Publication number Publication date
CN109554708A (en) 2019-04-02

Similar Documents

Publication Publication Date Title
CN109609953B (en) Ultra-limit copper alloy and preparation method thereof
CN109487195B (en) Ultra-limit iron alloy and preparation method thereof
CN109609952B (en) Ultra-limit magnesium alloy and preparation method thereof
CN109554707B (en) Ultra-limit aluminum alloy and preparation method thereof
CN109487196B (en) Ultra-limit nickel alloy and preparation method thereof
JP7242867B2 (en) Superalloy and its manufacturing method
CN109468639B (en) Ultra-limit zirconium alloy and preparation method thereof
CN104630686A (en) Preparation method of thermal barrier coating containing long-service-life antioxidant bonding layer
CN112176275B (en) Thermal barrier coating and preparation method and application thereof
CN107904543B (en) High-density copper alloy coating and preparation method thereof
CN105401116A (en) Preparation method for titanium alloy TiAl3-Al composite coating
CN109554708B (en) Ultra-limit titanium alloy and preparation method thereof
CN111962028A (en) EB-PVD/APS composite structure double-ceramic-layer thermal barrier coating and preparation method thereof
CN114525048B (en) Rare earth reinforced zirconia high-temperature oxidation resistant coating, coating and preparation method thereof
CN109023203B (en) Preparation method of stable crystalline hexaaluminate thermal barrier coating
CN111363998A (en) Preparation method of porous metal-ceramic nano composite thermal barrier coating
CN110607494B (en) Titanium alloy surface plasma spraying-electron beam cladding modified high-temperature oxidation resistant coating
CN1225568C (en) Technique for preparing metal-base ceramic composite coating by electric are spraying
CN106544615A (en) A kind of wear resistant corrosion resistant gradient coating magnesium alloy and preparation method thereof
CN109719414B (en) Ultra-limit tin alloy and preparation method thereof
WO2016058513A2 (en) Plasma-sprayed tin coating having excellent hardness and toughness, the preparation method therefor, and a mold coated with said tin coating
CN107385379B (en) A kind of preparation method of blast furnace energy recovery turbine blade surface corrosion-proof wear coating
CN114086102A (en) Ba (Mg)1/3Ta2/3)O3-YSZ double-ceramic-layer thermal barrier coating and preparation method thereof
CN108265260B (en) Preparation method of nickel-chromium-boron-silicon wear-resistant and fatigue-resistant coating
CN111058023A (en) Preparation method of cold spraying coating on glass surface

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant