CN106498355B - A kind of high temperature film sensor anti-oxidant composite armor and its manufacturing method - Google Patents

A kind of high temperature film sensor anti-oxidant composite armor and its manufacturing method Download PDF

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CN106498355B
CN106498355B CN201610913940.9A CN201610913940A CN106498355B CN 106498355 B CN106498355 B CN 106498355B CN 201610913940 A CN201610913940 A CN 201610913940A CN 106498355 B CN106498355 B CN 106498355B
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film sensor
zrb
temperature
insulating layers
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蒋洪川
王洪敏
赵晓辉
蒋书文
张万里
刘子良
黄敏
肖瑶
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University of Electronic Science and Technology of China
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Abstract

A kind of high temperature film sensor anti-oxidant composite armor and preparation method thereof, belongs to film sensor technologies field.The anti-oxidant composite armor is followed successively by BN insulating layers, ZrB from bottom to top2Base composite ceramic layer, Al2O3Coating, wherein BN insulating layers, ZrB2Base composite ceramic layer and Al2O3Coating is sequentially deposited to using the methods of evaporation or sputtering on thin film sensor sensitive function layer.The anti-oxidant composite armor of high temperature film sensor of the present invention, the antioxidant defense demand that the aero-engine high temperature film sensor under 1000~1700 DEG C of hot conditions can be met effectively increases stability, reliability and service life of the thin film sensor under high temperature and pressure adverse circumstances.

Description

A kind of high temperature film sensor anti-oxidant composite armor and its manufacturing method
Technical field
The invention belongs to film sensor technologies fields, especially with regard to aero-engine hot-end component surface state parameter The high temperature protection technology of test thin film sensor, this thin film sensor can be used for turbine engine combustion chamber inner wall and combustion gas, The accurate test of the state parameters such as temperature, the strain of the hot-end components such as turbine blade surface, designs for engine, verifies, optimizes Provide technical support.
Background technology
Aero-engine is known as the heart of aviation aircraft.When modern aeroengine works, due to turbo blade and Combustion chamber is in the adverse circumstances such as high temperature, high pressure, and turbo blade and combustor surface temperature are drastically increased while being generated larger Thermal strain, and the Temperature Distribution of turbo blade and combustor surface and strain are to the performance of turbogenerator and the influence in service life Greatly, and hot localised points existing for turbine blade surface can generate serious harm to the structural strength of turbo blade.Therefore, exist Modern aeroengine design and experimental study in, it is accurate measure under working condition the temperature of turbo blade and combustor surface and The performance parameters such as strain are most important to the design of engine.As aero-engine is constantly to high Mach, high thrust-weight ratio, Gao Ke Develop by the direction of property, hot-end component temperature is continuously improved, and residing environment is more and more severe.
Traditional measurement method is slotted in blade surface, and sheet, Filamentous sensor mount or embedment blade surface exist It destroys blade mechanical property, interference flowing field distribution, indeterminacy, layout the shortcomings of few, cannot be satisfied the high-temperature fines such as aero-engine The performance parameters such as temperature, stress, the strain of close structure member measure demand for development.Thin film sensor is to use thin film technique, will Sensitive material is deposited directly to blade surface, has multi-layer film structure thin film sensor by patterning process manufacture, has ruler Very little small (thickness is μm magnitude), light weight, thermal capacitance is small, fast response time, influences the advantages that smaller to the parts to be tested and environment, at For the developing direction of the high temperature component capabilities parameter measurement techniques such as current aeroengine combustor buring room, turbo blade.Currently, aviation Engine sensor, in terms of temperature measurement technology, thermocouple material system mainly have in, low temperature NiCr/NiSi systems K-type thermoelectricity It is even, high temperature PtRh/Pt systems S types, R type thermocouples；And under 1400 DEG C or more ultra-high temperature conditions, main material system is WRe systems Thermocouple；In strain testing technical aspect, strain gauge is made frequently with the materials such as NiCr, PdCr alloy and TaN nitride.These Sensitization functional material is all very sensitive to oxygen, high temperature, high pressure oxygen enrichment environment in, be easy to be oxidized by oxygen, causing property It can constantly fail and even fail.Therefore, how to realize that aero-engine thin film sensor has under the adverse circumstances of high temperature and pressure There is longer service life, be always the emphasis that domestic and foreign scholars are of interest and study, and develops novel fire resistant, anti-oxidant guarantor Sheath then becomes the key to solve the problem.
Common high-temperature oxidation resistant protective layer material Al2O3, it has, and high-melting-point, anti-oxidant, thermal stability is good and hypoxemia expands Dissipate the characteristics such as coefficient；One layer of Al is grown in sensitive function layer using evaporation or sputtering method2O3Film is as oxidation resistant protective layer Common method.But this method has the following disadvantages：First, Al2O3Protective layer can be isolated in external environment to a certain extent Oxygen to spreading inside film, substantially reduce the oxidation rate of sensitive function layer, but in Al2O3It is inevitably present in film Crystal defect, under high temperature environment Al2O3Oxygen can be by these defects slowly to sensitive function layer in protective layer or external environment Diffusion, causes functional layer to be aoxidized gradually at high temperature, to influence the performance of thin film sensor；Secondly as film-sensing Device working environment is severe, Al2O3The chemical stability of protective layer is not enough to resist the corrosion of aero-engine high-temperature fuel gas for a long time Property environment；In addition, in membrane-film preparation process or under the severe thermal shock working environment of aero-engine, Al2O3Protective layer Generation micro-crack may be induced due to stress, crackle becomes oxygen diffusion admittance so that protective layer antioxygenic property The coefficient of dispersion is very big, and reliability reduces, and then leads to component failure.Obvious single Al2O3Oxidation resistant protective layer cannot be satisfied high temperature The oxidation resistant growth requirement of thin film sensor.It is disclosed in the patent document of Publication No. CN102212823A《In alloy The method of thin film sensor is set on substrate》, patent of invention deposited oxide aluminium film on thin film sensor sensitive function layer As protective layer, under high temperature operating conditions, Al2O3Oxygen atom is spread to sensitive function layer in protective layer, and sensitive function layer also can It is gradually failed by oxidation, service life is shorter.It is disclosed in the patent document of Publication No. CN105675160A《Containing high temperature The W-Re film thermocouple sensor and preparation method of protective film group》, the patent of invention is in W-Re film thermocouple functional layer On be sequentially depositing the double protective layers of aluminum oxide film and amorphous silicon carbide film, enhance anti-oxidant and corrosion resistant performance, can be (1000~1700K) long-time measuring temperature signal under high temperature.But there are still deficiencies for the high temperature protection film group：At 1400 DEG C Under above hot conditions, carbonization silicon resistivity very little and it is conductive, at this point, aluminum oxide film layer high temperature resistance is special Property cannot be satisfied insulating requirements, can interfere the measurement of thin film sensor electric signal；In addition, at high temperature, aluminum oxide film is protected Oxygen atom is more serious to sensitive function layer diffusion phenomena in sheath so that its temperature limit is restricted, and cannot be satisfied Anti-oxidation protection demand under the conditions of higher temperature.
Invention content
In view of the defects in the background art, the present invention proposes a kind of anti-oxidant composite protectives of high temperature film sensor Layer and its manufacturing method can meet the anti-oxidant of under 1000~1700 DEG C of hot conditions aero-engine high temperature film sensor Protection requirements effectively increase stability, reliability and service life of the thin film sensor under high temperature and pressure adverse circumstances.
Above-mentioned purpose that the present invention is achieved by the following scheme：
A kind of anti-oxidant composite armor of high temperature film sensor, is followed successively by BN insulating layers, ZrB from bottom to top2Base is multiple Close ceramic layer, Al2O3Coating, wherein BN insulating layers, ZrB2Base composite ceramic layer and Al2O3Coating is using evaporation or sputtering The methods of be sequentially deposited on thin film sensor sensitive function layer.
Further, the thickness of the BN insulating layers is 10~20 μm, ZrB2The thickness of base composite ceramic layer is 20~50 μ M, Al2O3The thickness of coating is 2~5 μm.
Further, the ZrB2Base composite ceramic layer is Zr-B-Si-C films；It is prepared using sputtering method.
Further, the ZrB2When prepared by base composite ceramic layer, ZrB that the target that uses is inlayed for SiC2Composite target material, ZrB in target2Mass percent be 82wt%~88wt%, the mass percent of SiC is 12wt%~18wt%.
Further, the ZrB2When prepared by base composite ceramic layer, the target used alternately posts silicon chip and zirconium to be symmetrical The B of piece4C targets, wherein B4C, Si and Zr is 10 in the area ratio of sputter area:(2~3):(7~8).
A kind of high temperature film sensor preparation method of anti-oxidant composite armor, includes the following steps：
Step 1：On the sensitive function layer of thin film sensor, the BN using purity not less than 99.99wt% is used as target The method of rf magnetron sputtering sputters BN insulating layers；Wherein, back end vacuum degree is 10-3Pa hereinafter, operating air pressure be 0.2~ 1.2Pa, sputtering power are 100~300W, sputter gas N2With the mixed gas of Ar, underlayer temperature is 100~300 DEG C, lining Substrate biasing is 100V~200V, and the thickness for preparing BN insulating layers is 10~20 μm；
Step 2：On the BN insulating layers that step 1 deposits, Zr-B-Si-C films are deposited using radio frequency magnetron sputtering method； Wherein, back end vacuum degree is 10-3Pa hereinafter, operating air pressure be 0.4~1.2Pa, sputter gas Ar, Ar flow be 10~ 25sccm, sputtering power are 200~500W, and underlayer temperature is 300~500 DEG C, and substrate bias is 100~150V, the Zr- of preparation The thickness of B-Si-C films is 20~50 μm；The ZrB that the target used is inlayed for SiC2Composite target material, ZrB in target2Quality Percentage is 82wt%~88wt%, and the mass percent of SiC is 12wt%~18wt%, or alternately posts silicon using symmetrical The B of piece and zirconium piece4C targets, B4C, Si and Zr is 10 in the area ratio of sputter area:(2~3):(7~8)；
Step 3：On the Zr-B-Si-C films that step 2 deposits, high-purity Al targets with purity not less than 99.99wt% are Target, using the method for reactive sputtering, substrate temperature be 600~800 DEG C, vacuum degree 10-3To true under the conditions of Pa is below O is passed through in empty room2Mixing sputter gas to air pressure with Ar is 0.4~1.2Pa, O2Flow-rate ratio with Ar is 1:9~2:8, it prepares Obtain the Al of covering Zr-B-Si-C films2O3Layer (in the process, can be aoxidized on the surface layer of Zr-B-Si-C films, formed by Table and inner relatively thin ZrO2The pre-oxidation layer of gradient transition)；Then it is placed in vacuum annealing furnace, 10-3Pa is below It is made annealing treatment in vacuum environment, annealing temperature is 1000~1200 DEG C, and annealing soaking time is 2~5h, you can in Zr-B- The Al that thickness is 2~5 μm is formed on Si-C films2O3Coating；To obtain thin film sensor.
A kind of high temperature film sensor based on above-mentioned anti-oxidant composite armor, be followed successively by from bottom to top alloy substrate, NiCrAlY alloy transitions layer, thermally grown Al2O3Layer, Al2O3Insulating layer, sensitive function layer, BN insulating layers, ZrB2Base composite ceramic Layer and Al2O3Coating, wherein BN insulating layers, ZrB2Base composite ceramic layer and Al2O3Coating is using the methods of evaporation or sputtering It is sequentially deposited on thin film sensor sensitive function layer.
Further, the Al2O3One layer of BN insulating layer can also be set between insulating layer and sensitive function layer.
A kind of preparation method of the high temperature film sensor based on above-mentioned anti-oxidant composite armor, includes the following steps：
The surface treatment of step 1, Ni based alloy substrates：Ni based alloy substrate surfaces are processed by shot blasting first, then Successively the surface of alloy substrate is cleaned by ultrasonic using industrial degreaser, acetone, alcohol and deionized water, then uses nitrogen gun It dries up, drying residual moisture, using plasma cleaning base plate before plated film；
The preparation of step 2, NiCrAlY alloy transition layers：It is placed in back end by obtained Ni based alloy substrates are handled through step 1 Vacuum degree is 10-3In Pa vacuum environments below, using NiCrAlY alloys as target, argon gas is sputter gas, and sputtering pressure is Under conditions of 0.2~1.0Pa, sputtering power are 300~500W, base reservoir temperature is 400~500 DEG C, using the side of d.c. sputtering For method by NiCrAlY alloy depositions on through step 1 treated nickel-base alloy substrate, deposited film thickness is about 10~20 μm；
Step 3, thermally grown Al2O3The preparation of layer：The composite substrate obtained after step 2 processing is placed in vacuum heat In stove, it is higher than 5 × 10 in vacuum degree-4Aluminium is analysed under the high vacuum environment of Pa and 1000~1200 DEG C of temperature conditions handles 6~10h； Then, 1000~1200 DEG C of temperature are kept and are passed through oxygen to normal pressure, 5~10h of oxidation processes cools to room temperature with the furnace, obtains Band NiCrAlY transition zones and Al2O3The composite substrate of thermally grown layer；
Step 4, Al2O3The preparation of insulating layer：It is 10 that the composite substrate that gained is handled through step 3, which is placed in back end vacuum degree,-3Pa vacuum chambers below, under conditions of substrate temperature is 200~600 DEG C, using evaporation or sputtering method depositing Al2O3Absolutely Edge layer；Then, it places it in vacuum annealing furnace and is made annealing treatment, annealing temperature is 1000~1200 DEG C, annealing heat preservation Time is 2~5h, prepares Al2O3Thickness of insulating layer is 5~10 μm；
The preparation of step 5, the first BN insulating layers：On the composite substrate obtained after step 4, it is not less than with purity The BN of 99.99wt% is target, using radio frequency magnetron sputtering method in Al2O3The first BN insulating layers are sputtered on insulating layer；Wherein, Back end vacuum degree is 10-3For Pa hereinafter, operating air pressure is 0.2~1.2Pa, sputtering power is 100~300W, sputter gas N2With The mixed gas of Ar, underlayer temperature are 100~300 DEG C, and substrate bias is 100V~200V, control sputtering time, the of preparation One 5~20 μm of BN thickness of insulating layer；
The preparation of step 6, thin film sensor sensitive function layer：The composite substrate that step 5 obtains is placed in vacuum cavity, Thin film sensor sensitive function layer is prepared on the first BN insulating layers using the method for evaporation or sputtering；
The preparation of step 7, the 2nd BN insulating layers：On the composite substrate with sensitive function layer obtained after step 6, with BN of the purity not less than 99.99wt% is target, and the 2nd BN insulating layers are sputtered using the method for rf magnetron sputtering；Wherein, it carries on the back Bottom vacuum degree is 10-3For Pa hereinafter, operating air pressure is 0.2~1.2Pa, sputtering power is 100~300W, sputter gas N2And Ar Mixed gas, underlayer temperature be 100~300 DEG C, substrate bias be 100V~200V, prepare the 2nd BN insulating layers thickness be 10~20 μm；
Step 8, ZrB2The preparation of base composite ceramic layer：On the 2nd BN insulating layers that step 7 deposits, using radio frequency magnetron Sputtering method deposits Zr-B-Si-C films；Wherein, back end vacuum degree is 10-3Pa hereinafter, operating air pressure be 0.4~1.2Pa, splash Body of emanating is Ar, and Ar flows are 10~25sccm, and sputtering power is 200~500W, and underlayer temperature is 300~500 DEG C, and substrate is inclined Pressure is 100~150V, and the thickness of the Zr-B-Si-C films of preparation is 20~50 μm；The ZrB that the target used is inlayed for SiC2It is multiple Target is closed, ZrB in target2Mass percent be 82wt%~88wt%, the mass percent of SiC be 12wt%~ 18wt%, or using the symmetrical B for alternately posting silicon chip and zirconium piece4C targets, B4C, Si and Zr is in the area ratio of sputter area 10:(2~3):(7~8)；
Step 9, Al2O3The preparation of coating：On the Zr-B-Si-C films that step 8 deposits, it is not less than with purity High-purity Al targets of 99.99wt% are target, using the method for reactive sputtering, substrate temperature is 600~800 DEG C, vacuum degree is 10-3O is passed through into vacuum chamber under the conditions of Pa is below2Mixing sputter gas to air pressure with Ar is 0.4~1.2Pa, O2And Ar Flow-rate ratio be 1:9~2:8, the Al of covering Zr-B-Si-C films is prepared2O3Layer is (in the process, thin in Zr-B-Si-C The surface layer of film can be aoxidized, and relatively thin ZrO is formed from outward appearance to inner essence2The pre-oxidation layer of gradient transition)；Then it is placed on vacuum In annealing furnace, 10-3It is made annealing treatment in Pa vacuum environments below, annealing temperature is 1000~1200 DEG C, annealing heat preservation Time is 2~5h, you can the Al that thickness is 2~5 μm is formed on Zr-B-Si-C films2O3Coating；It is described thin to obtain Film sensors.
Beneficial effects of the present invention are：
1, the present invention proposes a kind of anti-oxidant composite armor structure of high temperature film sensor, from bottom to top successively For BN insulating layers, ZrB2Base composite ceramic layer, Al2O3Coating.Wherein, BN is shown due to extremely strong covalent bond characteristic Excellent high temperature insulation characteristic so that it still has very high resistivity at high temperature, can meet the insulation requirements under hot conditions； Secondly, coefficient of thermal expansion and the sensitization functional materials such as W-Re, platinum rhodium, palladium chromium of BN are not much different, and have preferable thermally matched, heat Stress is smaller, and adhesive force is good；Meanwhile the sensitization functional materials such as BN and W-Re, platinum rhodium, palladium chromium have good chemical compatibility Property, it will not react under the high temperature conditions, can effectively stop Al2O3Oxygen and sensitive function layer metal ion in insulating layer Diffusion；In addition, BN and ZrB2The similar thermal expansion coefficient of base composite ceramic layer, and the two has identical B element, it can in interface Bonding transition is formed, makes sensor that there is good adhesive force.
2, high temperature film sensor of the present invention ZrB in anti-oxidant composite armor2Base composite ceramic layer uses Zr-B- Si-C films have good high-temperature oxidation resistant, thermal shock resistance and strong corrosion resistant as oxidation resistant protective layer.First, exist In high-temperature oxidation process, in ZrB2The surface layer of base composite ceramic layer can successively generate sticky B2O3、SiO2Glass phase, the two can Form pyrex, the ZrO that filled composite ceramic layer superficial oxidation is formed2In skeleton and gap, continuous sticky cause is formed Close glass phase protective layer, the glass of these sticky densifications mutually can by VISCOUS FLOW come make up preparation, high-temperature oxydation or The defects of micro-crack generated, gap may be induced during anti-thermal shock, therefore the coating has good " self-healing " ability, So as to effectively stop Al2O3Coating and possible induction generation micro-crack expansion during preparation, high-temperature oxydation or anti-thermal shock It dissipates oxygen in channel internally to spread, composite ceramic layer is prevented further to be aoxidized, to play the role of protecting sensitive function layer； Secondly, the B of sticky densification2O3、SiO2In the surface layer skeleton of glass phase filled composite ceramic layer oxidation or gap, formed similar " armored concrete " structure has the ability that extremely strong high temperature resistance high-speed flow washes away；In addition, ZrB2Base composite ceramic layer has Strong corrosion resistant can effectively resist aero-engine fuel gas buring generation corrosive gas and invade anti-oxidant composite armor Erosion, extends the service life of anti-oxidant composite armor.
3, Al of the high temperature film sensor in anti-oxidant composite armor of the present invention2O3The controllable ZrB of coating2Base is multiple The partial pressure of oxygen of ceramic layer local environment is closed, active insulation oxygen environment is simultaneously in low oxygen partial pressure environment, significantly slows down Its oxidation rate；Secondly, ZrB can effectively be inhibited2Successively oxidation generates B to base composite ceramic layer under the high temperature conditions2O3、SiO2Glass Glass mutually with temperature increase and generate volatilization, while also avoid by its directly it is exposed in high-temperature high-speed airflow environment because washing away And cause the loss of glass phase, it is ensured that form continuous sticky dense glass phase under the high temperature conditions, fill ZrB2Base composite ceramic The patina skeleton of enamel coating simultaneously forms oxidation prevention layer, prevents ZrB2Base composite ceramic layer is further aoxidized.Therefore, Al2O3Covering Layer can not only improve ZrB2The service life of base composite ceramic layer, and under the premise of with identical service life, can have Effect reduces ZrB2The thickness of base composite ceramic layer film effectively prevents under superhigh temperature adverse circumstances to improve service life Lead to ZrB2Base composite ceramic layer is blocked up, to cause, stress is excessive and generates the phenomenon that falling off；Meanwhile giving high-temperature oxidation resistant layer Design and optimization provide bigger and more flexible elastic space.In addition, for ZrB in the present invention2Base composite ceramic layer is being adopted Al is prepared with reactive sputtering2O3During coating, part surface layer is aoxidized to form ZrO2From outward appearance to inner essence gradual transition Layer is pre-oxidized, which is ZrO2, with outermost Al2O3Coating similar thermal expansion coefficient can be formed good Thermal stress that is thermally matched, being generated under releasable hot conditions improves the adhesive force between film layer.
4, the present invention proposes a kind of anti-oxidant composite armor structure of high temperature film sensor, from bottom to top successively For BN insulating layers, ZrB2Base composite ceramic layer, Al2O3Coating；For the oxidation resistant protective layer single compared to structure, this is anti- Aoxidizing composite armor has multiple antioxidant defense, and the service life is longer, temperature applicable range higher, wider；Obtaining phase Under the premise of antioxidant effect and service life, the equivalent thickness of the compound anti-oxidation layer can be with smaller；These characteristics, not only Be conducive to the anti-oxidant ceramic thin sheet application of some superhigh temperature, and provided more to the design of high-temperature oxidation resistant layer and optimization Big and more flexible elastic space.
Description of the drawings
Fig. 1 is the structural schematic diagram of existing plural layers sensor；
Fig. 2 is a kind of structural schematic diagram of the thin film sensor based on the anti-oxidant composite armor of the present invention；
Fig. 3 is the sectional view for the W-Re thin film sensor based on the anti-oxidant composite armor of the present invention that embodiment provides； Wherein, 1 is Ni based alloy substrates, and 2 be NiCrAlY alloy transition layers, and 3 be thermally grown Al2O3Layer, 4 be Al2O3Insulating layer, 5 are First BN insulating layers, 6 be the positive negative thermal electrode of film thermocouple, and 7 be the 2nd BN insulating layers, and 8 be ZrB2Base composite ceramic layer, 9 are Al2O3Coating, wherein 7,8,9 layers constitute the anti-oxidant composite armor of the present invention.
Specific implementation mode
With reference to the accompanying drawings and examples, technical scheme of the present invention is described in detail.
Embodiment
As shown in figure 3, being the W-Re thin film sensor based on the anti-oxidant composite armor of the present invention that embodiment provides Sectional view；It is followed successively by Ni based alloys substrate 1, NiCrAlY alloy transitions layer 2, thermally grown Al from bottom to top2O3Layer 3, Al2O3Insulation The 4, the first BN insulating layers 5 of layer, the positive negative thermal electrode 6 of W-Re film thermocouple, the 2nd BN insulating layers 7, ZrB2Base composite ceramic layer 8, Al2O3Coating 9.
The preparation method for the W-Re thin film sensor based on the anti-oxidant composite armor of the present invention that embodiment provides, specifically Include the following steps：
The surface treatment of step 1, Ni based alloy substrates：Ni based alloy substrate surfaces are processed by shot blasting first, then Ultrasonic cleaning 15min is successively carried out to the surface of alloy substrate using industrial degreaser, acetone, alcohol and deionized water, then is used Nitrogen gun dries up, drying residual moisture, using plasma cleaning base plate 5min before plated film；
The preparation of step 2, NiCrAlY alloy transition layers：It is placed in back end by obtained Ni based alloy substrates are handled through step 1 Vacuum degree is 5.0 × 10-4In the vacuum environment of Pa, using NiCrAlY alloys as target, argon gas is sputter gas, and sputtering pressure is Under conditions of 0.4Pa, sputtering power 500W, base reservoir temperature are 450 DEG C, using the method for d.c. sputtering by NiCrAlY alloys It is deposited on through on step 1 treated nickel-base alloy substrate, deposited film thickness is about 15 μm；
Step 3, thermally grown Al2O3The preparation of layer：The composite substrate obtained after step 2 processing is placed in vacuum heat In stove, 5 × 10-4Aluminium is analysed under the high vacuum environment of Pa and 1000 DEG C of temperature conditions handles 10h；Then, 1000 DEG C of temperature are kept And oxygen is passed through to normal pressure, oxidation processes 6h cools to room temperature with the furnace, obtains band NiCrAlY transition zones and Al2O3Thermally grown layer Composite substrate；
Step 4, Al2O3The preparation of insulating layer：Will through step 3 handle gained composite substrate be placed in back end vacuum degree be 5 × 10-4The vacuum chamber of Pa, using high-purity Al target of the purity not less than 99.99wt% as target, O2With the mixed gas conduct of Ar Sputter gas, O2Flow-rate ratio with Ar is 1:9, sputtering pressure 0.3Pa, under conditions of substrate temperature is 400 DEG C, using reaction Sputtering method deposits the Al that a layer thickness is about 5 μm2O3Insulating layer；Then, it is 5.0 × 10 to place it in vacuum degree-4Pa's It is made annealing treatment in vacuum annealing furnace, annealing temperature is 1000 DEG C, and annealing soaking time is 2h, prepares Al2O3Thickness of insulating layer It is 5 μm；
The preparation of step 5, the first BN insulating layers：On the composite substrate obtained after step 4, it is not less than with purity The BN of 99.99wt% is target, using radio frequency magnetron sputtering method in Al2O3The first BN insulating layers are sputtered on insulating layer；Wherein, Back end vacuum degree is 5 × 10-4Pa, operating air pressure 0.6Pa, sputtering power 300W, sputter gas N2With the gaseous mixture of Ar Body, N2Flow-rate ratio with Ar is 2:8, underlayer temperature is 300 DEG C, substrate bias 150V, control sputtering time, the first of preparation BN thickness of insulating layer is about 10 μm；
The preparation of step 6, the positive negative thermal electrode of W-Re film thermocouple：With W-5wt%Re and W-26wt%Re alloy target materials For sputtering target material, using the method for the hard mask version that magnetically controlled DC sputtering matches with Z-shaped hole slot, by W-Re thermoelectricity Even positive electrode and negative electrode are successively deposited on through on step 5 treated the first BN insulating layers, two kinds of thin-film materials are in measured point Overlapped formation node；Wherein, specific process parameter：Back end vacuum degree 5 × 10-4Pa, operating air pressure 0.4Pa, sputtering power The flow of 150W, sputter gas Ar are 25sccm, and the parameters such as control sputtering time prepare the thickness of W-Re film thermocouple positive and negative anodes About 2 μm of degree；
The preparation of step 7, the 2nd BN insulating layers：In the composite substrate with W-Re film thermocouple obtained after step 6 On, the BN using purity not less than 99.99wt% is target, using the method for rf magnetron sputtering in Wolfram rhenium heat electric couple functional layer The 2nd BN insulating layers are sputtered, and cover Wolfram rhenium heat electric couple functional layer；Wherein, back end vacuum degree is 5 × 10-4Pa, operating air pressure are 0.6Pa, sputtering power 300W, sputter gas N2With the mixed gas of Ar, N2Flow-rate ratio with Ar is 2:8, underlayer temperature is 300 DEG C, substrate bias 150V, the thickness for preparing the 2nd BN insulating layers is about 10 μm；
Step 8, ZrB2The preparation of base composite ceramic layer：On the 2nd BN insulating layers that step 7 deposits, using radio frequency magnetron Sputtering method deposits Zr-B-Si-C films；Wherein, back end vacuum degree is 5 × 10-4Pa, operating air pressure 0.6Pa, sputter gas For Ar, Ar flows are 25sccm, and sputtering power 500W, underlayer temperature is 400 DEG C, substrate bias 150V, the Zr-B- of preparation The thickness of Si-C films is 30 μm；The ZrB that the target used is inlayed for SiC2Round composite target material, ZrB in target2Quality hundred Score is 82wt%~88wt%, and the mass percent of SiC is 12wt%~18wt%, or alternately posts silicon chip using symmetrical With the B of zirconium piece4C targets, B4C, Si and Zr is 10 in the area ratio of sputter area:(2~3):(7~8)；
Step 9, Al2O3The preparation of coating：On the Zr-B-Si-C films that step 8 deposits, it is not less than with purity High-purity Al targets of 99.99wt% are target, are 700 DEG C in substrate temperature, vacuum degree is 5 × 10 using the method for reactive sputtering- 4O is passed through under conditions of Pa into vacuum chamber2Mixing sputter gas to air pressure with Ar is 0.4Pa, O2Flow-rate ratio with Ar is 2: 8, the Al of covering Zr-B-Si-C films is prepared2O3(in the process, the surface layer of Zr-B-Si-C films can be aoxidized layer, shape At from outward appearance to inner essence relatively thin ZrO2The pre-oxidation layer of gradient transition, with Al2O3Coating similar thermal expansion coefficient can be formed good Good thermally matched, the thermal stress generated under releasable hot conditions improves the adhesive force between film layer)；Then it is placed on In vacuum annealing furnace, 5.0 × 10-4It is made annealing treatment in the vacuum environment of Pa, annealing temperature is 1000 DEG C, when annealing is kept the temperature Between be 2h, you can on Zr-B-Si-C films formed thickness be about 5 μm Al2O3Coating；To obtain with anti-oxidant compound The W-Re film thermocouple structure of protective layer.

Claims (9)

1. a kind of anti-oxidant composite armor of high temperature film sensor, including BN insulating layers, ZrB2Base composite ceramic layer, Al2O3 Coating, wherein BN insulating layers, ZrB2Base composite ceramic layer and Al2O3Coating is sequentially deposited to using evaporation or sputtering method On thin film sensor sensitive function layer, the ZrB2Base composite ceramic layer is Zr-B-Si-C films.
2. the anti-oxidant composite armor of high temperature film sensor according to claim 1, which is characterized in that the BN is exhausted The thickness of edge layer is 10~20 μm, ZrB2The thickness of base composite ceramic layer is 20~50 μm, Al2O3The thickness of coating is 2~5 μ m。
3. the anti-oxidant composite armor of high temperature film sensor according to claim 1, which is characterized in that the ZrB2 Base composite ceramic layer is prepared using sputtering method.
4. the anti-oxidant composite armor of high temperature film sensor according to claim 1, which is characterized in that the ZrB2 When prepared by base composite ceramic layer, ZrB that the target that uses is inlayed for SiC2Composite target material, ZrB in target2Mass percent be The mass percent of 82wt%~88wt%, SiC are 12wt%~18wt%.
5. the anti-oxidant composite armor of high temperature film sensor according to claim 1, which is characterized in that the ZrB2 When prepared by base composite ceramic layer, the target used is the symmetrical B for alternately posting silicon chip and zirconium piece4C targets, wherein B4C, Si and Zr It is 10 in the area ratio of sputter area:(2~3):(7~8).
6. a kind of high temperature film sensor preparation method of anti-oxidant composite armor, includes the following steps：
Step 1：On the sensitive function layer of thin film sensor, the BN using purity not less than 99.99wt% is target, using radio frequency The method of magnetron sputtering sputters BN insulating layers；Wherein, back end vacuum degree is 10-3Pa hereinafter, operating air pressure be 0.2~1.2Pa, splash It is 100~300W, sputter gas N to penetrate power2With the mixed gas of Ar, underlayer temperature is 100~300 DEG C, and substrate bias is 100V~200V, the thickness for preparing BN insulating layers are 10~20 μm；
Step 2：On the BN insulating layers that step 1 deposits, Zr-B-Si-C films are deposited using radio frequency magnetron sputtering method；Wherein, Back end vacuum degree is 10-3For Pa hereinafter, operating air pressure is 0.4~1.2Pa, sputter gas Ar, Ar flow is 10~25sccm, is splashed It is 200~500W to penetrate power, and underlayer temperature is 300~500 DEG C, and substrate bias is 100~150V, and the Zr-B-Si-C of preparation is thin The thickness of film is 20~50 μm；The ZrB that the target used is inlayed for SiC2Composite target material, ZrB in target2Mass percent be The mass percent of 82wt%~88wt%, SiC are 12wt%~18wt%, or alternately post silicon chip and zirconium piece using symmetrical B4C targets, B4C, Si and Zr is 10 in the area ratio of sputter area:(2~3):(7~8)；
Step 3：Step 2 deposit Zr-B-Si-C films on, using purity not less than 99.99wt% high-purity Al targets as target, Using the method for reactive sputtering, substrate temperature be 600~800 DEG C, vacuum degree 10-3Under the conditions of Pa is below into vacuum chamber It is passed through O2Mixing sputter gas to air pressure with Ar is 0.4~1.2Pa, O2Flow-rate ratio with Ar is 1:9~2:8, it is prepared and covers Cover the Al of Zr-B-Si-C films2O3Layer；Then it is placed in vacuum annealing furnace, 10-3In Pa vacuum environments below into Row annealing, annealing temperature are 1000~1200 DEG C, and annealing soaking time is 2~5h, you can the shape on Zr-B-Si-C films The Al for being 2~5 μm at thickness2O3Coating；To obtain thin film sensor.
7. a kind of high temperature film sensor based on anti-oxidant composite armor described in claim 1, is followed successively by conjunction from bottom to top Gold base, NiCrAlY alloy transitions layer, thermally grown Al2O3Layer, Al2O3Insulating layer, sensitive function layer, BN insulating layers, ZrB2Base is multiple Close ceramic layer and Al2O3Coating, wherein BN insulating layers, ZrB2Base composite ceramic layer and Al2O3Coating is using evaporation or sputtering Method is sequentially deposited on thin film sensor sensitive function layer.
8. high temperature film sensor according to claim 7, which is characterized in that the Al2O3Insulating layer and sensitive function layer Between be arranged one layer of BN insulating layer.
9. a kind of preparation method of the high temperature film sensor based on anti-oxidant composite armor described in claim 1, including with Lower step：
The surface treatment of step 1, Ni based alloy substrates：Ni based alloy substrate surfaces are processed by shot blasting first, are then used Industrial degreaser, acetone, alcohol and deionized water are successively cleaned by ultrasonic the surface of alloy substrate, then are blown with nitrogen gun It does, drying residual moisture, using plasma cleaning base plate before plated film；
The preparation of step 2, NiCrAlY alloy transition layers：It is placed in back end vacuum by obtained Ni based alloy substrates are handled through step 1 Degree is 10-3In Pa vacuum environments below, using NiCrAlY alloys as target, argon gas is sputter gas, sputtering pressure is 0.2~ It, will using the method for d.c. sputtering under conditions of 1.0Pa, sputtering power are 300~500W, base reservoir temperature is 400~500 DEG C For NiCrAlY alloy depositions on through step 1 treated nickel-base alloy substrate, deposited film thickness is 10~20 μm；
Step 3, thermally grown Al2O3The preparation of layer：The composite substrate obtained after step 2 processing is placed in vacuum heat treatment furnace, It is higher than 5 × 10 in vacuum degree-4Aluminium is analysed under the vacuum environment of Pa and 1000~1200 DEG C of temperature conditions handles 6~10h；Then, it protects It holds 1000~1200 DEG C of temperature and is passed through oxygen to normal pressure, 5~10h of oxidation processes cools to room temperature with the furnace, obtains band NiCrAlY transition zones and Al2O3The composite substrate of thermally grown layer；
Step 4, Al2O3The preparation of insulating layer：It is 10 that the composite substrate that gained is handled through step 3, which is placed in back end vacuum degree,-3Pa with Under vacuum chamber, substrate temperature be 200~600 DEG C under conditions of, using evaporation or sputtering method depositing Al2O3Insulating layer；So Afterwards, it places it in vacuum annealing furnace and is made annealing treatment, annealing temperature is 1000~1200 DEG C, and annealing soaking time is 2 ~5h prepares Al2O3Thickness of insulating layer is 5~10 μm；
The preparation of step 5, the first BN insulating layers：On the composite substrate obtained after step 4, it is not less than with purity The BN of 99.99wt% is target, using radio frequency magnetron sputtering method in Al2O3The first BN insulating layers are sputtered on insulating layer；Wherein, Back end vacuum degree is 10-3For Pa hereinafter, operating air pressure is 0.2~1.2Pa, sputtering power is 100~300W, sputter gas N2With The mixed gas of Ar, underlayer temperature are 100~300 DEG C, and substrate bias is 100V~200V, the first BN thickness of insulating layer of preparation 5~20 μm；
The preparation of step 6, thin film sensor sensitive function layer：The composite substrate that step 5 obtains is placed in vacuum cavity, is used The method of evaporation or sputtering prepares thin film sensor sensitive function layer on the first BN insulating layers；
The preparation of step 7, the 2nd BN insulating layers：On the composite substrate with sensitive function layer obtained after step 6, with purity BN not less than 99.99wt% is target, and the 2nd BN insulating layers are sputtered using the method for rf magnetron sputtering；Wherein, back end is true Reciprocal of duty cycle is 10-3For Pa hereinafter, operating air pressure is 0.2~1.2Pa, sputtering power is 100~300W, sputter gas N2With mixing for Ar Close gas, underlayer temperature be 100~300 DEG C, substrate bias be 100V~200V, prepare the 2nd BN insulating layers thickness be 10~ 20μm；
Step 8, ZrB2The preparation of base composite ceramic layer：On the 2nd BN insulating layers that step 7 deposits, using rf magnetron sputtering Method deposits Zr-B-Si-C films；Wherein, back end vacuum degree is 10-3Pa hereinafter, operating air pressure be 0.4~1.2Pa, sputter gas Body is Ar, and Ar flows are 10~25sccm, and sputtering power is 200~500W, and underlayer temperature is 300~500 DEG C, and substrate bias is The thickness of 100~150V, the Zr-B-Si-C films of preparation are 20~50 μm；The ZrB that the target used is inlayed for SiC2Composition target Material, ZrB in target2Mass percent be 82wt%~88wt%, the mass percent of SiC is 12wt%~18wt%, or Person is using the symmetrical B for alternately posting silicon chip and zirconium piece4C targets, B4C, Si and Zr is 10 in the area ratio of sputter area:(2~3): (7~8)；
Step 9, Al2O3The preparation of coating：On the Zr-B-Si-C films that step 8 deposits, 99.99wt% is not less than with purity High-purity Al targets be target, using the method for reactive sputtering, substrate temperature be 600~800 DEG C, vacuum degree 10-3Pa or less Under conditions of O is passed through into vacuum chamber2Mixing sputter gas to air pressure with Ar is 0.4~1.2Pa, O2Flow-rate ratio with Ar is 1:9~2:8, the Al of covering Zr-B-Si-C films is prepared2O3Layer；Then it is placed in vacuum annealing furnace, 10- 3It is made annealing treatment in Pa vacuum environments below, annealing temperature is 1000~1200 DEG C, and annealing soaking time is 2~5h, i.e., The Al that thickness is 2~5 μm can be formed on Zr-B-Si-C films2O3Coating；To obtain the thin film sensor.
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