CN111996482A - Titanium alloy with amorphous thermal barrier coating deposited on surface and preparation method thereof - Google Patents

Titanium alloy with amorphous thermal barrier coating deposited on surface and preparation method thereof Download PDF

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Publication number
CN111996482A
CN111996482A CN202010887780.1A CN202010887780A CN111996482A CN 111996482 A CN111996482 A CN 111996482A CN 202010887780 A CN202010887780 A CN 202010887780A CN 111996482 A CN111996482 A CN 111996482A
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titanium alloy
amorphous
thermal barrier
barrier coating
deposited
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冯晶
杨凯龙
郑奇
王一涛
汪俊
张志东
李振军
王峰
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Shaanxi Tianxuan Coating Technology Co ltd
Kunming University of Science and Technology
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Shaanxi Tianxuan Coating Technology Co ltd
Kunming University of Science and Technology
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Priority to CN202010887780.1A priority Critical patent/CN111996482A/en
Publication of CN111996482A publication Critical patent/CN111996482A/en
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Abstract

The invention relates to the technical field of thermal barrier coatings, and particularly discloses a titanium alloy with an amorphous thermal barrier coating deposited on the surface and a preparation method thereof, wherein an HVOF method or a supersonic electric arc spraying method is used for depositing a bonding layer on a titanium alloy substrate, and the thickness of the bonding layer is 100-200 μm; depositing an amorphous ceramic coating on the bonding layer by adopting an EB-PVD method, wherein the thickness of the amorphous ceramic coating is 200-300 mu m; the technological parameters are as follows: the air pressure in the cabin is not higher than 3 x 10‑6Pa; the deposition rate is not lower than 10 nm/min; the rotation speed of the sample stage is not lower than 45 r/min. The patent obtains a titanium alloy with an amorphous thermal barrier coating deposited on the surface, and the titanium alloy has extremely low thermal conductivity (< 1.15 W.m)‑1·K‑1) Therefore, the use temperature of the titanium alloy can be increased to 200-400 ℃ above the melting point of the original titanium alloy matrix, so that the titanium alloy can be used in an environment with the temperature exceeding the melting point of the titanium alloy.

Description

Titanium alloy with amorphous thermal barrier coating deposited on surface and preparation method thereof
Technical Field
The invention relates to the technical field of thermal barrier coatings, in particular to a titanium alloy with an amorphous thermal barrier coating deposited on the surface 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.
The thermal barrier coating technology is characterized in that a layer of ceramic with excellent heat insulation performance is deposited on a metal substrate to reduce the temperature of the substrate, and in addition, the metal substrate can be isolated from a high-temperature and high-corrosion environment due to the existence of the ceramic coating, so that the risk of oxidation and corrosion of the metal substrate is greatly reduced, and a device (such as an engine turbine blade) made of the thermal barrier coating can operate at high temperature.
Rare earth niobium/tantalate ceramics (RENb/TaO)4) The high melting point and the low thermal conductivity (1.38-1.94 W.m.)-1.K-1) High coefficient of thermal expansion (11X 10)-6K-11200 ℃ and the iron elastic toughness, and the like, and is considered as a new generation of thermal barrier coating material with the most potential. The ferroelastic toughening mechanism endows the rare earth niobium/tantalate ceramic with excellent high-temperature fracture toughness, which is a unique advantage that other potential thermal barrier coating materials do not have; the use of the material in the field of thermal barrier coatings is also under study, and how to maximize the protective effect of the ceramic coating on the titanium alloy substrate is still the focus of the current study.
Disclosure of Invention
The invention provides a titanium alloy with an amorphous thermal barrier coating deposited on the surface and a preparation method thereof, so as to obtain a titanium alloy material which has lower thermal conductivity and meets the use requirement in a high-temperature environment.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the titanium alloy with the amorphous thermal barrier coating deposited on the surface comprises a titanium alloy substrate, wherein a bonding layer and an amorphous ceramic coating are sequentially deposited on the surface of the titanium alloy substrate.
The technical principle and the effect of the technical scheme are as follows:
1. the titanium alloy deposited with the amorphous ceramic coating in the scheme has extremely low thermal conductivity (< 1.15 W.m)-1·K-1) Thus, the service temperature of the titanium alloy can be raised to the original titanium alloy matrixThe melting point is 200-400 ℃ above, so that the titanium alloy can be used in the environment with the temperature exceeding the melting point.
2. According to the scheme, the bonding layer can improve the bonding effect between the amorphous ceramic layer and the titanium alloy matrix, improve the adhesive force of the surface ceramic layer and avoid the falling off of the coating caused by external force; and the bonding layer is used as a transition layer between the titanium alloy substrate and the amorphous ceramic coating, so that the risk of coating falling caused by thermal expansion mismatching of the titanium alloy substrate and the amorphous ceramic coating in a high-temperature environment is reduced.
3. The hindrance heat that amorphous ceramic coating can be fine in this scheme is by the coating surface to the diffusion of titanium alloy base member, reduce titanium alloy surface temperature, improve titanium alloy service temperature, the reason is that, its inside atom of amorphous ceramic coating is unordered range, the diffuse reflection effect has been formed to the phonon, make the heat on amorphous ceramic coating surface reflected to all sides, compare in the crystal state ceramic coating of traditional orderly arrangement simultaneously, there is not the grain boundary or looks interface inside the amorphous ceramic coating, so to speak such structure can avoid some defects, the introduction of face defect etc. make the performance of coating have very big promotion.
Furthermore, the bonding layer is MCrAlY, and M is Ni or Co.
Has the advantages that: in the NiCrAlY and CoCrAlY materials, the proportion of each element is different, and the obtained bonding effect and the thermal expansion coefficient are different, so that the titanium alloy with different components and different thermal expansion can be matched.
Further, the amorphous ceramic coating component is RETaO4One or a mixture of several of them.
Has the advantages that: the rare earth tantalate has low thermal conductivity, the thermal expansion coefficient is close to that of titanium alloy, and the special iron-elastic phase change of the rare earth tantalate can reduce the risk of coating shedding caused by poor phase change volume of the ceramic coating under the high-temperature condition, so the rare earth tantalate is the first choice of the amorphous ceramic coating; moreover, the rare earth tantalate has high reflection coefficient, so that the reflection effect on thermal radiation is excellent, and the temperature of the titanium alloy matrix in a high-temperature environment is greatly reduced, so that the service temperature of the titanium alloy is increased; the rare earth tantalate has higher hardness and fracture toughness, can resist the impact of sand and stones in the atmospheric environment, ensure the integrity of the coating and avoid the occurrence of microcracks.
Further, the thickness of the bonding layer is 100-200 mu m, and the thickness of the amorphous ceramic coating is 200-300 mu m.
Has the advantages that: the best performance of each coating in the range is obtained through experimental tests.
The application also discloses a preparation method of the titanium alloy with the amorphous thermal barrier coating deposited on the surface, which comprises the following steps:
step 1: depositing an adhesive layer on the titanium alloy substrate by using an HVOF method or a supersonic electric arc spraying method, wherein the thickness of the adhesive layer is 100-200 mu m;
step 2: depositing an amorphous ceramic coating on the bonding layer by adopting an EB-PVD method, wherein the thickness of the amorphous ceramic coating is 200-300 mu m; wherein the EB-PVD method comprises the following process parameters: the air pressure in the cabin is not higher than 3 x 10-6Torr; the deposition rate is not lower than 10 nm/min; the rotation speed of the sample stage is not lower than 45 r/min.
Has the advantages that: the EB-PVD high-energy electron beam can process materials at a higher temperature, almost all substances can be evaporated, the high-efficiency deposition rate of the coating is guaranteed, the amorphous ceramic coating is obtained under the technological parameters of the scheme through experimental verification, in addition, the high-energy electron beam power is easy to adjust, the beam spot size and position are easy to control, and the coating thickness can be accurately controlled.
Further, the titanium alloy substrate in step 1 needs to be subjected to surface degreasing and impurity removal treatment before the coating is deposited.
Has the advantages that: the surface impurities of the base material are reduced, and the adhesion between the base material and the adhesive layer can be improved.
Further, in the step 1, sand blasting is needed to be carried out on the titanium alloy substrate before the coating is deposited, and the surface roughness of the titanium alloy substrate after sand blasting is 30-40 μm.
Has the advantages that: the sand blasting can improve the surface strength of the base material, and the roughness is set to be 30-40 mu m, so that the bonding between the bonding layer and the titanium alloy base body is facilitated.
Further, an HVOF method is adopted in the step 1, wherein the technological parameters are that the oxygen flow is not lower than 2150SCFH, the kerosene flow is not lower than 18.25LPH, the carrier gas is 13.0SCFH, the powder feeding amount is not lower than 5RPM, and the spraying distance is not more than 200 mm.
Further, the ceramic raw material used for the amorphous ceramic coating in the step 2 is a rare earth tantalate block, and the size of the block is 2-3 mm.
Has the advantages that: the rare earth tantalate block with the size of 2-3 mm not only ensures that the rare earth tantalate block cannot be knocked away by high-energy electron beams due to the fact that the size of the block target is too small, but also ensures that coating components cannot be uneven due to the fact that the size of the target is too large.
Further, the rare earth tantalate block is formed by sintering rare earth tantalate powder at high temperature, the particle size of the rare earth tantalate powder is 20-30 microns, the high-temperature sintering temperature is 1100-1200 ℃, and the sintering time is 8-10 hours.
Has the advantages that: the proper sintering temperature can keep the blank body in certain compactness, so that the components of the rare earth tantalate are more uniform, and the occurrence of a second phase is avoided, thereby ensuring the stable evaporation rate of EB-PVD and more uniform coating components.
Drawings
FIG. 1 is a diffraction pattern of an amorphous ceramic coating obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the amorphous ceramic coating obtained in example 1 of the present invention.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1:
the titanium alloy with the amorphous thermal barrier coating deposited on the surface comprises a titanium alloy substrate, wherein the titanium alloy is TC4 titanium alloy, a bonding layer and an amorphous ceramic coating are sequentially deposited on the titanium alloy substrate, the bonding layer is NiCrAlY, the thickness of the bonding layer is 100 mu m, and the amorphous ceramic coating is YTaO4The thickness of the amorphous ceramic coating was 200 μm.
The preparation process of the titanium alloy with the amorphous thermal barrier coating deposited on the surface comprises the following steps:
step 1: removing oil stains and impurities on the surface of the TC4 titanium alloy substrate by using a soaking method, treating by using ultrasonic oscillation, washing by using deionized water, and drying; and performing sand blasting treatment on the TC4 titanium alloy matrix, wherein the surface roughness after sand blasting is 40 mu m.
Depositing a bonding layer with the thickness of 100 mu m on the surface of the TC4 titanium alloy matrix subjected to sand blasting by utilizing an HVOF method, wherein the HVOF method comprises the following process parameters: the powder particle diameter is 20-40 μm, the oxygen flow is 2150SCFH, the kerosene flow is 18.25LPH, the carrier gas is 13.0SCFH, the powder feeding amount is 5RPM, and the spraying distance is 200 mm.
Step 2: an amorphous ceramic coating is deposited on the bonding layer by adopting an EB-PVD method, and the thickness of the amorphous ceramic coating is 200 mu m; wherein the EB-PVD method comprises the following process parameters: the air pressure in the cabin is not higher than 3 x 10-6Torr; the deposition rate is not lower than 10 nm/min; the rotation speed of the sample stage is not lower than 45 r/min.
Wherein the ceramic raw material used for the amorphous ceramic coating is YTaO4A block body with the size of 2-3 mm, and the preparation process comprises the step of preparing spherical YTaO with the particle size of 20-30 mu m4Pressing the powder into a raw sheet blank with the diameter of 15mm and the thickness of 1.5mm, sintering at 1100-1200 ℃ for 8-10 h, and crushing into blocks with the thickness of 2-3 mm.
And finally, treating the amorphous ceramic coating by using a polishing machine to ensure that the surface roughness of the amorphous ceramic coating reaches 4-6 microns.
Examples 2 to 10:
the difference from example 1 is that the thickness or the composition of the coating layers in examples 2 to 10 are different, and the specific difference is shown in Table 1.
Table 1 shows the thickness and composition of the adhesive layer and the amorphous ceramic coating in examples 2 to 10, "- -" in the table indicates nothing
Figure BDA0002656083550000041
Figure BDA0002656083550000051
Example 11:
the difference from embodiment 1 is that the amorphous ceramic coating in this embodiment comprises YTaO4And DyTaO4Two components, the coating thickness is 200 μm.
Example 12:
the difference from embodiment 1 is that the amorphous ceramic coating in this embodiment comprises YTaO4、DyTaO4、NdTaO4And LuTaO4Four ceramic components, the thickness of the coating being 200 μm.
Comparative example 1:
the difference from example 1 is that in step 2 of comparative example 1, spherical YTaO having a particle size of 20 to 30 μm is formed by APS method4The powder is deposited on the bonding layer to form a crystalline ceramic coating with orderly arranged atomic sequences, and the thickness of the ceramic coating is 200 mm.
The following experimental tests are carried out by selecting examples 1-12 and comparative example 1:
1. XRD phase test analysis
XRD phase test analysis is carried out on the surfaces of the samples obtained in examples 1-12 and comparative example 1, and by taking example 1 as an example, as shown in figure 1, as can be seen from figure 1, a diffraction pattern has an obvious unit steamed bread peak which is the expression that a phase is an amorphous component, so that the conclusion that a coating prepared by adopting parameters of EB-PVD in step 2 is an amorphous coating can be obtained.
2. Analysis of scanning electron microscope morphology
By taking the example 1 as an example, it can be seen from fig. 2 that the amorphous ceramic coating obtained in the example 1 has a columnar shape, and the columnar shape can improve the strain tolerance of the thermal barrier coating, reduce the internal stress of the coating, hinder the expansion of microcracks, prevent the coating from falling off and failing due to thermal mismatch, and prolong the service life of the coating.
3. Thermal conductivity detection
The samples obtained in examples 1-12 and comparative example 1 were selected and tested by a laser thermal conductivity meter, and at a temperature of 800K, the test results of examples 1-12 are shown in the following table 2, while the comparative example 1 tested a thermal conductivity of 1.87W.m-1·K-1。
Table 2 shows the thermal conductivities (W.m.) of examples 1 to 12-1·K-1)
Figure BDA0002656083550000061
From table 2 above, it follows that:
the titanium alloy deposited with the amorphous ceramic coating has extremely low thermal conductivity (< 1.15 W.m)-1·K-1) Therefore, the use temperature of the titanium alloy can be increased to 200-400 ℃ above the melting point of the original titanium alloy matrix, so that the titanium alloy can be used in the environment with the temperature exceeding the melting point of the titanium alloy.
The foregoing is merely an example of the present invention and common general knowledge of the known specific materials and characteristics thereof has not been described herein in any greater extent. It should be noted that, for those skilled in the art, without departing from 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 (10)

1. The titanium alloy with the amorphous thermal barrier coating deposited on the surface comprises a titanium alloy substrate and is characterized in that a bonding layer and an amorphous ceramic coating are sequentially deposited on the surface of the titanium alloy substrate.
2. The titanium alloy with an amorphous thermal barrier coating deposited on the surface thereof as claimed in claim 1, wherein: the bonding layer comprises MCrAlY, and M is Ni or Co.
3. The titanium alloy with an amorphous thermal barrier coating deposited on the surface as claimed in claim 2, wherein: the amorphous ceramic coating comprises RETaO4One or a mixture of several of them.
4. The titanium alloy with an amorphous thermal barrier coating deposited on the surface as claimed in claim 3 wherein: the thickness of the bonding layer is 100-200 mu m, and the thickness of the amorphous ceramic coating is 200-300 mu m.
5. Method for preparing a titanium alloy with an amorphous thermal barrier coating deposited on its surface according to claim 4, characterized in that: the method comprises the following steps:
step 1: depositing an adhesive layer on the titanium alloy substrate by using an HVOF method or a supersonic electric arc spraying method, wherein the thickness of the adhesive layer is 100-200 mu m;
step 2: depositing an amorphous ceramic coating on the bonding layer by adopting an EB-PVD method, wherein the thickness of the amorphous ceramic coating is 200-300 mu m; wherein the EB-PVD method comprises the following process parameters: the air pressure in the cabin is not higher than 3 x 10-6Torr; the deposition rate is not lower than 10 nm/min; the rotation speed of the sample stage is not lower than 45 r/min.
6. The method for preparing titanium alloy with amorphous thermal barrier coating deposited on the surface according to claim 5, wherein: in the step 1, the titanium alloy substrate is subjected to surface degreasing and impurity treatment before the coating is deposited.
7. The method for preparing titanium alloy with amorphous thermal barrier coating deposited on the surface according to claim 5, wherein: and in the step 1, sand blasting is carried out on the titanium alloy matrix before the coating is deposited, and the surface roughness of the titanium alloy matrix after sand blasting is 30-40 mu m.
8. The method for preparing titanium alloy with amorphous thermal barrier coating deposited on the surface according to claim 5, wherein: the HVOF method is adopted in the step 1, wherein the technological parameters are that the oxygen flow is not less than 2150SCFH, the kerosene flow is not less than 18.25LPH, the carrier gas is 13.0SCFH, the powder feeding amount is not less than 5RPM, and the spraying distance is not more than 200 mm.
9. The method for preparing titanium alloy with amorphous thermal barrier coating deposited on the surface according to claim 5, wherein: and 2, the ceramic raw material used for the amorphous ceramic coating in the step 2 is a rare earth tantalate block, and the size of the block is 2-3 mm.
10. The method for preparing a titanium alloy with an amorphous thermal barrier coating deposited on the surface according to claim 9, wherein: the rare earth tantalate block is formed by sintering rare earth tantalate powder at high temperature, the particle size of the rare earth tantalate powder is 20-30 mu m, the high-temperature sintering temperature is 1100-1200 ℃, and the sintering time is 8-10 hours.
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