CN108893740B - Method for preparing high-temperature insulating film by liquid-gas phase alternate deposition - Google Patents
Method for preparing high-temperature insulating film by liquid-gas phase alternate deposition Download PDFInfo
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- 230000008021 deposition Effects 0.000 title claims abstract description 46
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- 238000007740 vapor deposition Methods 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000011810 insulating material Substances 0.000 claims abstract description 14
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- 239000007789 gas Substances 0.000 claims description 18
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- 238000001540 jet deposition Methods 0.000 claims description 11
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- 238000002156 mixing Methods 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 5
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- B05D1/00—Processes for applying liquids or other fluent materials
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention discloses a method for preparing a high-temperature insulating film by liquid-gas phase alternate deposition, belongs to the technical field of advanced manufacturing, and relates to a method for preparing a high-temperature insulating film by liquid-gas phase alternate deposition. In the method, liquid phase deposition and gas phase deposition steps are alternately adopted, and insulating materials are deposited on the surface of a to-be-tested part layer by layer. Preparing liquid slurry of an insulating material, depositing the liquid slurry on a test piece to be tested according to a specific thickness by adopting a liquid phase deposition method, and drying and sintering at a high temperature to obtain an insulating layer I; then depositing a II insulating layer on the I insulating layer by adopting a vapor deposition method; and repeating the liquid phase deposition step and the gas phase deposition step alternately for many times by analogy, and finally obtaining the high-temperature insulating film with the required thickness. The high-temperature insulating film prepared by the method has the characteristics of compact structure, controllable thickness, good insulativity and stability and the like, and the insulation resistance of the insulating film at high temperature is effectively improved.
Description
Technical Field
The invention belongs to the technical field of advanced manufacturing, and relates to a method for preparing a high-temperature insulating film by liquid-gas phase alternate deposition.
Background
The high-temperature film sensor is a special sensor for measuring physical quantities or chemical quantities such as strain, heat flow, temperature, pressure, components and the like in a high-temperature environment, and mainly structurally comprises an insulating film, a sensitive layer and a protective layer. Wherein, the function of the insulating film is to realize the electric insulation of the tested piece and the sensitive layer. The high-quality insulating film is a key structure of the high-temperature film sensor, and the electrical conduction between the tested piece and the sensitive layer caused by the defects of the insulating film damages the basic condition of correctly acquiring and outputting the tested electric signal of the sensor, thereby causing the complete failure of the sensor.
The insulating film material of the high-temperature film sensor is generally various high-temperature resistant oxide ceramics, nitride ceramics, boride ceramics, carbide ceramics and the like, or composite ceramics consisting of two or more of the above ceramic materials. The ceramic insulating film can be prepared by various methods such as magnetron sputtering, electron beam/ion beam deposition, physical/chemical vapor deposition, thermal oxidation growth and the like. Generally, increasing the film thickness and reducing the film defects are two effective ways to increase the resistance of the insulating film. The documents Gao J, Duan F L, Yu C, et al, electric insulation of center of fine metallic air-electrode for high temperature sensor applications [ J]The preparation method of yttria-stabilized zirconia (YSZ) high-temperature insulating film is reported, in order to raise the high-temperature insulating resistance of YSZ film, the thickness of YSZ insulating film is increased to 500 micrometers by adopting thermal plasma spraying process, and its insulating resistance in 1300 deg.C environment is greater than or equal to 10k omega. However, in process practice, excessive film thickness tends to introduce more process defects inside the film, increasing the risk of cracking failure of the insulating film in high temperature environments. In the measurement of mechanical parameters of a high-temperature component, the excessively thick insulating film can also increase the length of a path transmitted to a sensitive layer to be measured, reduce the sensitivity of the sensor and cause additional interference to a test environment. On the other hand, the insulating film with compact structure and strong thermal shock resistance is also beneficial to improving the insulating resistance of the insulating film. The documents Niu D, Wang Q, Zhang C, etal.Preparation,characterization and application of high-temperature Al2O3,insulating film[J].Surface&Coating Technology,2016,291:318-2O3Transition layer, and final dual ion beam sputtering to deposit Al2O3The Al with compact structure and total thickness of about 4 μm is obtained by the composite process of the film2O3However, the maximum insulation resistance of the insulating thin film is only 8.4 k.OMEGA.at 800 ℃ because the total film thickness is too small. Therefore, although the film prepared by the thermal growth and sputtering process has high density and fewer defects, the total thickness of the film is relatively small due to process limitation, the high-temperature insulating property of the insulating film is difficult to improve, and excessive internal stress is generated inside the film due to the increase of the sputtering thickness, so that the insulating film is cracked at high temperature or peeled from the substrate. Therefore, how to improve the density of the film structure and increase the thickness of the film moderately through a reasonable preparation process is the key point for improving the performance of the high-temperature insulating film.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and invents a method for preparing a high-temperature insulating film by liquid-gas phase alternate deposition. The method alternately adopts liquid phase deposition and vapor deposition steps, the insulating material is deposited on the surface of a to-be-tested part layer by layer, a structural layer of the insulating film is obtained through liquid phase deposition, defects such as holes and cracks in the liquid phase deposition structural layer are filled through vapor deposition, and the prepared high-temperature insulating film has the characteristics of compact structure, controllable thickness, good insulating property and stability and the like.
The technical scheme adopted by the invention is as follows: a method for preparing a high-temperature insulating film by liquid-vapor alternate deposition is characterized in that liquid-vapor alternate deposition and vapor deposition steps are alternately adopted in the method, insulating materials are deposited on the surface of a to-be-tested part layer by layer, a structure layer of the insulating film is obtained by liquid-phase deposition, and the vapor deposition is adopted to fill up the defects of holes and cracks in the liquid-phase deposition structure layer, so that the high-temperature insulating film with compact structure, controllable thickness, good insulating property and high stability is obtained; firstly, mixing an insulating material into a liquid dispersant in the form of powder, sol or solution to prepare liquid slurry, depositing the liquid slurry on a tested piece according to a specific thickness by adopting a single or multiple liquid phase deposition method, and drying and sintering at a high temperature to obtain an insulating layer I; then depositing a II insulating layer on the I insulating layer by adopting a vapor deposition method; depositing the liquid slurry on the insulating layer II by adopting a single or multiple liquid phase deposition method, and drying and sintering at high temperature to obtain an insulating layer III; depositing an IV insulating layer on the III insulating layer by adopting a vapor deposition method again; repeating the liquid phase deposition step and the gas phase deposition step alternately for multiple times by analogy, and finally obtaining the high-temperature insulating film with the required thickness; the method comprises the following specific steps:
first, preparing insulating slurry
Firstly, mixing an insulating material in the form of powder, sol or solution into a liquid dispersant to prepare liquid slurry, wherein the insulating material comprises one or more of oxide ceramic, nitride ceramic, boride ceramic or carbide ceramic, or composite ceramic consisting of two or more ceramic materials; the liquid dispersant comprises one or more mixed liquid of water, organic matter/inorganic matter aqueous solution and liquid organic matter; the insulating ceramic liquid slurry can be in the form of one or more liquid mixtures of solution, sol, gel, suspension, turbid liquid, emulsion and paste;
second, liquid phase deposition of the insulating layer blank
The liquid phase deposition method is a method for depositing a liquid medium on the surface of the tested piece to form a functional or decorative metal, nonmetal or compound coating, and comprises but is not limited to one or more of spin coating, casting, printing, coating, screen printing, electric jet deposition, atomized spraying, electrophoretic deposition, lifting deposition and the like; uniformly depositing the prepared insulating slurry on the surface of a test piece by a liquid phase deposition method to obtain an insulating layer blank I with the thickness of 50-5000 nm,
thirdly, drying the insulating layer blank I
Drying the insulating layer I blank in an environment with the temperature of 20-500 ℃ to volatilize liquid components in the insulating layer I blank in a gaseous state to obtain a dried insulating layer I blank;
fourthly, controlling the thickness of the insulating layer blank I
Repeating the second step and the third step for multiple times until the thickness of the insulating layer blank I reaches a set value;
fifthly, sintering the blank of the insulating layer I
According to the sintering requirements of different ceramic materials, the high-temperature environment is one or a combination of a vacuum state, an air atmosphere, an oxygen atmosphere, a nitrogen atmosphere or an inert gas atmosphere; placing the dried insulating layer I blank in a high-temperature environment at the temperature of 300-1500 ℃ for sintering, and controlling the sintering temperature and the sintering time to obtain an insulating layer I with specific physical and chemical properties;
sixthly, depositing a II th insulating layer by vapor deposition
The vapor deposition method is a method for forming functional or decorative metal, nonmetal or compound coating on the surface of a workpiece by utilizing physical and chemical processes which occur in vapor phase, and comprises but is not limited to one or more methods of physical vapor deposition, chemical vapor deposition or epitaxial film deposition; depositing a II insulating layer with the thickness of 50-5000 nm on the surface of the sintered I insulating layer by adopting a vapor deposition method; the vapor deposition material is one or more of oxide ceramic, nitride ceramic, boride ceramic or carbide ceramic, or composite ceramic consisting of two or more of the above ceramic materials;
seventhly, repeating the liquid-gas alternate deposition step
Repeating the second to sixth steps until a high temperature insulating film of a desired thickness is obtained.
The invention has the following remarkable effects: the method for preparing the high-temperature insulating film by liquid-vapor alternate deposition can make up the defects of holes, cracks and the like introduced into the film structure in the film preparation process layer by layer and reduce the internal stress of the film. The high-temperature insulating film prepared by the method has a compact structure and controllable thickness, has good electrical insulating property and physical and chemical stability in a high-temperature environment, and effectively improves the insulating resistance of the insulating film at high temperature.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a high-temperature insulating film by liquid-gas alternating deposition according to the present invention, wherein: 1-a test piece, 2-an I insulating layer uniformly deposited by a liquid phase deposition method, 3-a II insulating layer uniformly deposited by a vapor phase deposition method, 4-a III insulating layer uniformly deposited by a liquid phase deposition method, 5-an IV insulating layer uniformly deposited by a vapor phase deposition method, n-an n-1 insulating layer uniformly deposited by a liquid phase deposition method, and n + 1-an n insulating layer uniformly deposited by a vapor phase deposition method.
Fig. 2 is a comparison graph of insulation resistance values of an alumina insulation film prepared only by an electro-jet deposition method and an alumina-silicon nitride composite insulation film prepared by a method for preparing a high-temperature insulation film by liquid-gas alternating deposition according to the present invention at an environment of 25 to 1200 ℃, wherein: 1-the insulation resistance value of the alumina insulation film prepared by adopting the electro-jet deposition method at the environment of 25-1200 ℃, 2-the insulation resistance value of the alumina-silicon nitride composite insulation film prepared by adopting the method for preparing the high-temperature insulation film by adopting the liquid-gas alternative deposition method at the environment of 25-1200 ℃.
FIG. 3 is a comparison graph of insulation resistance values of an alumina insulation film prepared only by an electro-jet deposition method and an alumina-silicon nitride composite insulation film prepared by a method for preparing a high-temperature insulation film by liquid-gas alternating deposition according to the present invention in a high-temperature environment of 1100-1200 ℃, wherein: 1-the insulation resistance value of the alumina insulation film prepared by adopting the electro-jet deposition method at the temperature of 1100-1200 ℃, and 2-the insulation resistance value of the alumina-silicon nitride composite insulation film prepared by adopting the method for preparing the high-temperature insulation film by adopting the liquid-gas alternative deposition method at the temperature of 1100-1200 ℃.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
In this embodiment, the insulating material is selected to be alumina ceramic, and first, alumina insulating slurry is prepared. And performing liquid phase deposition on the I insulating layer blank on the to-be-tested piece by adopting an electric jet deposition method, and drying and sintering the I insulating layer blank. Depositing a second insulating layer on the surface of the sintered first insulating layer by adopting a vapor deposition method; and repeating the liquid-gas alternate deposition step until the high-temperature insulating film with the ideal thickness is obtained.
FIG. 1 is a schematic diagram of a method for preparing a high-temperature insulating film by liquid-gas alternating deposition according to the present invention, and as shown in the figure, the method specifically comprises the following steps:
firstly, preparing alumina insulating slurry
Selecting an insulating material as alumina ceramic, selecting a liquid dispersant as absolute ethyl alcohol, preparing insulating material liquid slurry into a suspension, and mixing the alumina ceramic into the absolute ethyl alcohol in a powder form to prepare alumina suspension;
secondly, preparing the insulating layer blank I by adopting an electric jet deposition method
Selecting a liquid phase deposition method as electro-jet deposition, and uniformly depositing the prepared alumina insulation slurry on the surface of a to-be-tested piece by the electro-jet deposition method to obtain an alumina I insulating layer blank with the thickness of 50 nm;
thirdly, drying the insulating layer blank I
Placing the to-be-tested part deposited with the aluminum oxide insulating layer blank on a constant temperature heating table, and drying for 10min at the temperature of 500 ℃; volatilizing liquid components in the aluminum oxide insulating layer blank in a gaseous state to obtain a dried insulating layer I blank;
fourthly, controlling the thickness of the insulating layer blank I
Repeating the second step and the third step for 10 times until the thickness of the aluminum oxide insulating layer blank reaches 500 nm;
fifthly, sintering the blank of the insulating layer I
Selecting a sintering high-temperature environment as an air atmosphere, placing the dried aluminum oxide insulating layer blank in the air atmosphere at the temperature of 1500 ℃ for constant-temperature sintering for 1 hour to obtain an I insulating layer which has stable physical and chemical properties and is made of aluminum oxide;
sixthly, depositing a II th insulating layer by adopting a vapor deposition method
Selecting a vapor deposition material as silicon nitride ceramic, and depositing silicon nitride with the thickness of 50nm on the surface of the sintered I insulating layer by adopting a vapor deposition method to be used as a II insulating layer;
seventh, repeating the liquid-vapor phase alternate deposition step
Repeating the second to sixth steps until obtaining the alumina-silicon nitride composite high-temperature insulating film with the total thickness of 10 mu m.
FIG. 2 is a comparison graph of insulation resistance values of an alumina insulation film prepared by only adopting an electro-jet deposition method and an alumina-silicon nitride composite insulation film prepared by the method for preparing a high-temperature insulation film by liquid-gas alternating deposition of the invention at the temperature of 25-1200 ℃. FIG. 3 is a comparison graph of insulation resistance values of an alumina insulation film prepared by only adopting an electric jet method and an alumina-silicon nitride composite insulation film prepared by the method for preparing a high-temperature insulation film by liquid-gas alternating deposition of the invention under the high-temperature environment of 1100-1200 ℃. As can be seen from FIG. 2, the resistance value of the insulation film prepared by the method for preparing the high-temperature insulation film by liquid-gas alternating deposition is obviously higher than that of the alumina insulation film prepared by only adopting the electric jet method. As can be seen from fig. 3, when the temperature reaches 1200 ℃, the insulation resistance value of the alumina insulation film prepared by the electro-fluidic method is 38K Ω, while the insulation resistance value of the alumina-silicon nitride composite insulation film prepared by the method for preparing a high-temperature insulation film by liquid-gas alternating deposition according to the present invention is 54K Ω, which is 41% higher than that of the film.
The method for preparing the high-temperature insulating film by liquid-vapor alternate deposition can make up the defects of holes, cracks and the like introduced into the film structure in the film preparation process layer by layer and reduce the internal stress of the film. The high-temperature insulating film prepared by the method has the advantages of compact structure, controllable thickness, good insulativity and stability and the like, and provides a new technical method for improving the insulation resistance value of the insulating film at high temperature.
Claims (1)
1. A method for preparing a high-temperature insulating film by liquid-vapor alternate deposition is characterized in that liquid-vapor alternate deposition and vapor deposition steps are alternately adopted in the method, insulating materials are deposited on the surface of a to-be-tested part layer by layer, a structure layer of the insulating film is obtained by liquid-phase deposition, and the vapor deposition is adopted to fill up the defects of holes and cracks in the liquid-phase deposition structure layer, so that the high-temperature insulating film with compact structure, controllable thickness, good insulating property and high stability is obtained; firstly, mixing an insulating material into a liquid dispersant in the form of powder, sol or solution to prepare liquid slurry, then depositing the liquid slurry on a tested piece according to a specific thickness by adopting a single or multiple liquid phase deposition method, and drying and sintering at a high temperature to obtain an insulating layer I; then depositing a II insulating layer on the I insulating layer by adopting a vapor deposition method; depositing the liquid slurry on the insulating layer II by adopting a single or multiple liquid phase deposition method, and drying and sintering at high temperature to obtain an insulating layer III; depositing an IV insulating layer on the III insulating layer by adopting a vapor deposition method again; repeating the liquid phase deposition step and the gas phase deposition step alternately for multiple times by analogy, and finally obtaining the high-temperature insulating film with the required thickness; the method comprises the following specific steps:
first, preparing insulating slurry
Firstly, mixing an insulating material in the form of powder, sol or solution into a liquid dispersant to prepare liquid slurry, wherein the insulating material comprises one or more of oxide ceramic, nitride ceramic, boride ceramic or carbide ceramic, or composite ceramic consisting of two or more ceramic materials; the liquid dispersant comprises one or more mixed liquid of water, organic matter/inorganic matter aqueous solution and liquid organic matter; the insulating ceramic liquid slurry can be in the form of one or more liquid mixtures of solution, gel, suspension, turbid liquid, emulsion and paste;
second, liquid phase deposition of the insulating layer blank
The liquid phase deposition method is a method for depositing a liquid medium on the surface of a tested piece to form a functional or decorative compound coating, and comprises but is not limited to one or more of spin coating, casting, printing, coating, screen printing, electro-jet deposition, atomized spraying, electrophoretic deposition, lifting deposition and the like; uniformly depositing the prepared insulating slurry on the surface of a tested piece by a liquid phase deposition method to obtain an insulating layer blank I with the thickness of 50-5000 nm,
thirdly, drying the insulating layer blank I
Drying the insulating layer I blank in an environment with the temperature of 20-500 ℃ to volatilize liquid components in the insulating layer I blank in a gaseous state to obtain a dried insulating layer I blank;
fourthly, controlling the thickness of the insulating layer blank I
Repeating the second step and the third step for multiple times until the thickness of the insulating layer blank I reaches a set value;
fifthly, sintering the blank of the insulating layer I
According to the sintering requirements of different ceramic materials, the high-temperature environment is one or a combination of a vacuum state, an air atmosphere, an oxygen atmosphere, a nitrogen atmosphere or an inert gas atmosphere; placing the dried insulating layer I blank in a high-temperature environment at the temperature of 300-1500 ℃ for sintering, and controlling the sintering temperature and the sintering time to obtain an insulating layer I with specific physical and chemical properties;
sixthly, depositing a II th insulating layer by vapor deposition
The vapor deposition method is a method for forming a functional or decorative compound coating on the surface of a workpiece by utilizing physical and chemical processes which occur in a vapor phase, and comprises but is not limited to one or more methods of physical vapor deposition, chemical vapor deposition or epitaxial film deposition; depositing a II insulating layer with the thickness of 50-5000 nm on the surface of the sintered I insulating layer by adopting a vapor deposition method; the vapor deposition material is one or more of oxide ceramic, nitride ceramic, boride ceramic or carbide ceramic, or composite ceramic consisting of two or more of the above ceramic materials;
seventhly, repeating the liquid-gas alternate deposition step
Repeating the second to sixth steps until a high temperature insulating film of a desired thickness is obtained.
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