CN106498355A - A kind of high temperature film sensor antioxidation composite armor and its manufacture method - Google Patents

A kind of high temperature film sensor antioxidation composite armor and its manufacture method Download PDF

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CN106498355A
CN106498355A CN201610913940.9A CN201610913940A CN106498355A CN 106498355 A CN106498355 A CN 106498355A CN 201610913940 A CN201610913940 A CN 201610913940A CN 106498355 A CN106498355 A CN 106498355A
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thin film
zrb
vacuum
film sensor
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CN106498355B (en
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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 antioxidation composite armor and preparation method thereof, belongs to film sensor technologies field.The antioxidation composite armor is followed successively by BN insulating barriers, ZrB from bottom to top2Base composite ceramic layer, Al2O3Coating, wherein, BN insulating barriers, ZrB2Base composite ceramic layer and Al2O3Coating is sequentially deposited on thin film sensor sensitive function layer using the method such as evaporation or sputtering.High temperature film sensor antioxidation composite armor of the present invention, the antioxidant defense demand of aero-engine high temperature film sensor under 1000～1700 DEG C of hot conditionss can be met, stability of the thin film sensor under High Temperature High Pressure adverse circumstances, reliability and life-span is effectively increased.

Description

A kind of high temperature film sensor antioxidation composite armor and its manufacture method
Technical field
The invention belongs to film sensor technologies field, especially with regard to aero-engine hot-end component apparent condition parameter The high temperature protection technology of test thin film sensor, this thin film sensor can be used for turbine engine combustion chamber inwall and combustion gas, The accurate test of the state parameters such as the temperature of the hot-end components such as turbine blade surface, strain, designs, verifies, optimizes for electromotor Provide technical support.
Background technology
Aero-engine is described as the heart of aviation aircraft.When modern aeroengine works, due to turbo blade and In the adverse circumstances such as high temperature, high pressure, turbo blade and combustor surface temperature are drastically raised while producing larger combustor Thermal strain, and the impact in the performance of the Temperature Distribution of turbo blade and combustor surface and strain to turbogenerator and life-span Greatly, and the hot localised points that exist of turbine blade surface can produce serious harm to the structural strength of turbo blade.Therefore, exist In modern aeroengine design and experimental study, accurately under measurement working condition the temperature of turbo blade and combustor surface and The performance parameters such as strain are most important to the design of electromotor.As aero-engine is constantly to high Mach, high thrust-weight ratio, Gao Ke Direction by property is developed, and its hot-end component temperature is improved constantly, and residing environment is more and more severe.
Traditional measurement method is slotted in blade surface, and lamellar, thread sensor mount or embedment blade surface are present Destruction blade mechanical property, interference flowing field distribution, indeterminacy, the shortcomings of layout few, it is impossible to meet the high-temperature fines such as aero-engine The performance parameters such as the temperature of close structure member, stress, strain measure demand for development.Thin film sensor is to adopt thin film technique, will Sensitive material is deposited directly to blade surface, there is multi-layer film structure thin film sensor by patterning process manufacture, with chi Very little little (thickness be μm magnitude), light weight, little thermal capacitance, fast response time, to UUT and less environmental effect the advantages of, into Developing direction for the high temperature component capabilities parameter measurement techniques such as current aeroengine combustor buring room, turbo blade.At present, aviation Engine sensor, in terms of temperature measurement technology, during thermocouple material system mainly has, low temperature NiCr/NiSi systems K-type thermoelectricity Even, high temperature PtRh/Pt systems S types, R type thermocouples；And more than 1400 DEG C under ultra-high temperature condition, main material system is WRe systems Thermocouple；In strain testing technical elements, strain gauge is made frequently with the material such as NiCr, PdCr alloy and TaN nitride.These Sensitization functional material is all very sensitive to oxygen, in high temperature, the oxygen enrichment environment of high pressure, is easily oxidized by oxygen, causing property Can constantly fail.Therefore, how to realize that aero-engine thin film sensor has under the adverse circumstances of High Temperature High Pressure There are longer service life, always the Chinese scholars emphasis with research of interest, and develop novel fire resistant, antioxidation and protect Sheath then becomes the key of solve problem.
Conventional high-temperature oxidation resistant protective layer material Al2O3, it has high-melting-point, antioxidation, heat stability good and hypoxia expands The characteristics such as scattered coefficient；One layer of Al is grown in sensitive function layer using evaporation or sputtering method2O3Thin film as oxidation resistant protective layer is Common method.But this method has the following disadvantages：First, Al2O3Protective layer can be isolated in external environment condition to a certain extent Oxygen to thin film diffusion inside, significantly reduce the oxidation rate of sensitive function layer, but in Al2O3It is inevitably present in thin film Crystal defect, in high temperature environments Al2O3In protective layer or external environment, oxygen can pass through these defects lentamente to sensitive function layer Diffusion, causes functional layer gradually oxidized at high temperature, so as to affect the performance of thin film sensor；Secondly as film-sensing Device work under bad environment, Al2O3The chemical stability of protective layer is not enough to the corrosion that long-time resists aero-engine high-temperature fuel gas Property environment；Additionally, in membrane-film preparation process or under the severe thermal shock working environment of aero-engine, Al2O3Protective layer Generation micro-crack is induced because of stress, and crackle becomes oxygen diffusion admittance so that protective layer antioxygenic property The coefficient of dispersion is very big, and reliability reduces, and then causes component failure.Obviously single Al2O3Oxidation resistant protective layer cannot meet high temperature The antioxidative growth requirement of thin film sensor.Disclose in the patent documentation of Publication No. CN102212823A《In alloy The method that 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, Al2O3In protective layer, oxygen atom is spread to sensitive function layer, and sensitive function layer also can Gradually oxidized and fail, service life is shorter.Disclose in the patent documentation of Publication No. CN105675160A《Contain high temperature The W-Re film thermocouple sensor of protective film group and preparation method》, 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, strengthen antioxidation and corrosion resistant performance, can be (1000～1700K) long-time measurement temperature signal under high temperature.But the high temperature protection thin film group still suffers from deficiency：At 1400 DEG C Under above hot conditionss, carbonization silicon resistivity very little and there is electric conductivity, now, aluminum oxide film layer high temperature resistance is special Property cannot meet insulating requirements, can disturb the measurement of the thin film sensor signal of telecommunication；Additionally, at high temperature, aluminum oxide film is protected In sheath, oxygen atom is more serious to sensitive function layer diffusing phenomenon so that its temperature limit is restricted, it is impossible to meet Anti-oxidation protection demand under the conditions of higher temperature.
Content of the invention
A kind of defect that the present invention is present for background technology, it is proposed that high temperature film sensor antioxidation composite protective Layer and its manufacture method, can meet the antioxidation of aero-engine high temperature film sensor under 1000～1700 DEG C of hot conditionss Protection requirements, effectively increase stability of the thin film sensor under High Temperature High Pressure adverse circumstances, reliability and life-span.
The present invention employs the following technical solutions the above-mentioned purpose that is achieved：
A kind of high temperature film sensor antioxidation composite armor, is followed successively by BN insulating barriers, ZrB from bottom to top2Base is multiple Close ceramic layer, Al2O3Coating, wherein, BN insulating barriers, ZrB2Base composite ceramic layer and Al2O3Coating using evaporation or is sputtered It is sequentially deposited on thin film sensor sensitive function layer etc. method.
Further, the thickness of the BN insulating barriers 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 thin film；Prepared using sputtering method.
Further, the ZrB2When prepared by base composite ceramic layer, the ZrB that the target for adopting 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 for adopting posts silicon chip and zirconium for symmetrical alternating The B of piece4C targets, wherein, B4C, Si and Zr are 10 in the area ratio of sputter area:(2～3):(7～8).
A kind of high temperature film sensor preparation method of antioxidation composite armor, comprises the following steps：
Step 1：On the sensitive function layer of thin film sensor, the BN of 99.99wt% is not less than as target with purity, is adopted The method sputtering BN insulating barriers of rf magnetron sputtering；Wherein, back end vacuum is 10-3Below Pa, operating air pressure be 0.2～ 1.2Pa, sputtering power are 100～300W, and sputter gas are 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 barriers is 10～20 μm；
Step 2：On the BN insulating barriers of step 1 deposition, Zr-B-Si-C thin film is deposited using radio frequency magnetron sputtering method； Wherein, back end vacuum is 10-3Below Pa, operating air pressure are 0.4～1.2Pa, and sputter gas are Ar, Ar flows are 10～ 25sccm, sputtering power are 200～500W, and underlayer temperature is 300～500 DEG C, and substrate bias are 100～150V, the Zr- of preparation The thickness of B-Si-C thin film is 20～50 μm；The ZrB that the target for adopting is inlayed for SiC2Composite target material, ZrB in target2Quality Percent is 82wt%～88wt%, and the mass percent of SiC is 12wt%～18wt%, or posts silicon using symmetrical alternating Piece and the B of zirconium piece4C targets, B4C, Si and Zr are 10 in the area ratio of sputter area:(2～3):(7～8)；
Step 3：On the Zr-B-Si-C thin film of step 2 deposition, with high-purity Al targets that purity is not less than 99.99wt% it is Target, using the method for reactive sputtering, substrate temperature be 600～800 DEG C, vacuum be 10-3To true under conditions of below Pa 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, prepare Obtain the Al for covering Zr-B-Si-C thin film2O3Layer (in the process, can oxidized on the top layer of Zr-B-Si-C thin film, formation by Table and inner relatively thin ZrO2The pre-oxidation layer of gradient transition)；Then it is placed in vacuum annealing furnace, 10-3Below Pa's Made annealing treatment in vacuum environment, annealing temperature is 1000～1200 DEG C, annealing temperature retention time is 2～5h, you can in Zr-B- The Al that thickness is 2～5 μm is formed on Si-C thin film2O3Coating；So as to obtain thin film sensor.
A kind of high temperature film sensor based on above-mentioned antioxidation composite armor, be followed successively by from bottom to top alloy substrate, NiCrAlY alloy transition layers, thermally grown Al2O3Layer, Al2O3Insulating barrier, sensitive function layer, BN insulating barriers, ZrB2Base composite ceramic Layer and Al2O3Coating, wherein, BN insulating barriers, ZrB2Base composite ceramic layer and Al2O3Coating is using the method such as evaporation or sputtering It is sequentially deposited on thin film sensor sensitive function layer.
Further, the Al2O3One layer of BN insulating barrier can also be set between insulating barrier and sensitive function layer.
A kind of preparation method of the high temperature film sensor based on above-mentioned antioxidation composite armor, comprises the following steps：
Step 1, the surface treatment of Ni based alloy substrates：First Ni based alloy substrate surfaces are processed by shot blasting, then Successively the surface of alloy substrate is cleaned by ultrasonic using industrial degreaser, acetone, ethanol and deionized water, then uses nitrogen gun Dry up, dry residual moisture, using plasma cleaning base plate before plated film；
Step 2, the preparation of NiCrAlY alloy transition layers：The Ni based alloy substrates obtained through step 1 process are placed in back end Vacuum is 10-3In the vacuum environment of below Pa, with NiCrAlY alloys as target, argon is sputter gas, and sputtering pressure is 0.2～1.0Pa, sputtering power be 300～500W, base reservoir temperature be 400～500 DEG C under conditions of, using the side of d.c. sputtering On nickel-base alloy substrate of the method by NiCrAlY alloy depositions after processing through step 1, about 10～20 μm of deposited film thickness；
Step 3, thermally grown Al2O3The preparation of layer：The composite base plate obtained after processing through step 2 is placed in vacuum heat In stove, it is higher than 5 × 10 in vacuum-4Under the high vacuum environment of Pa and 1000～1200 DEG C of temperature conditionss, analysis aluminum processes 6～10h； Then, 1000～1200 DEG C of temperature are kept and oxygen is passed through to normal pressure, 5～10h of oxidation processes, cool to room temperature with the furnace, obtain Band NiCrAlY transition zones and Al2O3The composite base plate of thermally grown layer；
Step 4, Al2O3The preparation of insulating barrier：The composite base plate for processing gained through step 3 is placed in back end vacuum for 10-3The vacuum chamber of below Pa, under conditions of substrate temperature is 200～600 DEG C, using evaporation or sputtering method depositing Al2O3Absolutely Edge layer；Then, place it in vacuum annealing furnace and made annealing treatment, annealing temperature is 1000～1200 DEG C, annealing insulation Time is 2～5h, prepares Al2O3Thickness of insulating layer is 5～10 μm；
Step 5, the preparation of BN insulating barriers：On the composite base plate obtained after through step 4, it is not less than with purity The BN of 99.99wt% is target, using radio frequency magnetron sputtering method in Al2O3BN insulating barriers are sputtered on insulating barrier；Wherein, Back end vacuum is 10-3Below Pa, operating air pressure are 0.2～1.2Pa, and sputtering power is 100～300W, and sputter gas are N2With The mixed gas of Ar, underlayer temperature are 100～300 DEG C, and substrate bias are 100V～200V, control sputtering time, the of preparation One 5～20 μm of BN thickness of insulating layer；
Step 6, the preparation of thin film sensor sensitive function layer：The composite base plate that step 5 is obtained is placed in vacuum cavity, Thin film sensor sensitive function layer is prepared on BN insulating barriers using the method for evaporation or sputtering；
Step 7, the preparation of the 2nd BN insulating barriers：On the composite base plate with sensitive function layer obtained after through step 6, with It is target that purity is not less than the BN of 99.99wt%, sputters the 2nd BN insulating barriers using the method for rf magnetron sputtering；Wherein, carry on the back Bottom vacuum is 10-3Below Pa, operating air pressure are 0.2～1.2Pa, and sputtering power is 100～300W, and sputter gas are N2And Ar Mixed gas, underlayer temperature be 100～300 DEG C, substrate bias be 100V～200V, prepare the 2nd BN insulating barriers thickness be 10～20 μm；
Step 8, ZrB2The preparation of base composite ceramic layer：On the 2nd BN insulating barriers of step 7 deposition, using radio frequency magnetron Sputtering method deposits Zr-B-Si-C thin film；Wherein, back end vacuum is 10-3Below Pa, operating air pressure are 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 Press as 100～150V, the thickness of the Zr-B-Si-C thin film of preparation is 20～50 μm；The ZrB that the target for adopting is inlayed for SiC2Multiple Close target, ZrB in target2Mass percent be 82wt%～88wt%, the mass percent of SiC be 12wt%～ 18wt%, or using symmetrically alternately posting the B of silicon chip and zirconium piece4C targets, B4C, Si and Zr in the area ratio of sputter area are 10:(2～3):(7～8)；
Step 9, Al2O3The preparation of coating：On the Zr-B-Si-C thin film of step 8 deposition, it is not less than with purity High-purity Al targets of 99.99wt% are target, using the method for reactive sputtering, substrate temperature be 600～800 DEG C, vacuum be 10-3O is passed through into vacuum room under conditions of below Pa2Mixing sputter gas to air pressure with Ar is 0.4～1.2Pa, O2And Ar Flow-rate ratio be 1:9～2:8, prepare the Al for covering Zr-B-Si-C thin film2O3Layer is (in the process, thin in Zr-B-Si-C The top layer of film can be oxidized, forms from outward appearance to inner essence relatively thin ZrO2The pre-oxidation layer of gradient transition)；Then vacuum is placed on In annealing furnace, 10-3Made annealing treatment in the vacuum environment of below Pa, annealing temperature is 1000～1200 DEG C, annealing insulation Time is 2～5h, you can form the Al that thickness is 2～5 μm on Zr-B-Si-C thin film2O3Coating；Described thin so as to obtain Film sensors.
Beneficial effects of the present invention are：
1st, the present invention proposes a kind of high temperature film sensor antioxidation composite protective Rotating fields, and which is from bottom to top successively For BN insulating barriers, ZrB2Base composite ceramic layer, Al2O3Coating.Wherein, BN is because showing with extremely strong covalent bond characteristic Excellent high temperature insulation characteristic so which still has very high resistivity at high temperature, can meet the insulation requirements under hot conditionss； Secondly, the thermal coefficient of expansion of BN is more or less the same with sensitization functional materials such as W-Re, platinum rhodium, palladium chromium, with preferably thermally matched, heat Stress is less, and adhesive force is good；Meanwhile, BN has good chemical compatibility with sensitization functional materials such as W-Re, platinum rhodium, palladium chromium Property, will not also react under the high temperature conditions, can effectively stop Al2O3Oxygen and sensitive function layer metal ion in insulating barrier Diffusion；Additionally, BN and ZrB2The similar thermal expansion coefficient of base composite ceramic layer, and both have identical B element, can in interface Bonding transition is formed, makes sensor that there is good adhesive force.
2nd, high temperature film sensor of the present invention ZrB in antioxidation composite armor2Base composite ceramic layer adopts Zr-B- Used as oxidation resistant protective layer, which has good high-temperature oxidation resistant, thermal shock resistance and strong corrosion resistant to Si-C thin film.First, exist In high-temperature oxidation process, in ZrB2The top 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 the middle of skeleton and space, continuously sticky cause is formed Close glass phase protective layer, these sticky fine and close glass mutually can be made up by VISCOUS FLOW preparing, high-temperature oxydation or The defects such as micro-crack, the space of generation may be induced during anti-thermal shock, and therefore the coating has good " self-healing " ability, So as to can effectively stop Al2O3Coating and possible induction generation micro-crack expansion during preparation, high-temperature oxydation or anti-thermal shock In scattered passage, oxygen internally spreads, and prevents composite ceramic layer further oxidized, so as to play a part of to protect sensitive function layer； Secondly, sticky fine and close B2O3、SiO2In the middle of the top layer skeleton of glass phase filled composite ceramic layer oxidation or space, formed similar " armored concrete " structure, possesses the ability that extremely strong high temperature resistance high velocity air washes away；Additionally, ZrB2Base composite ceramic layer has Strong corrosion resistant, can effectively resist aero-engine fuel gas buring generation corrosive gas and antioxidation composite armor is invaded Erosion, extends the service life of antioxidation composite armor.
3rd, Al of the high temperature film sensor in antioxidation composite armor of the present invention2O3Coating controllable ZrB2Base 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 suppressed2First rear oxidation generates B to base composite ceramic layer under the high temperature conditions2O3、SiO2Glass Glass with temperature raise and produce volatilization, while also avoid by its directly exposed in high-temperature high-speed airflow environment because washing away And cause the loss of glass phase, it is ensured that form continuously 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 oxidized.Therefore, Al2O3Cover Layer not only can improve ZrB2The service life of base composite ceramic layer, and on the premise of with identical service life, can have Effect reduces ZrB2The thickness of base composite ceramic layer film, effectively prevent under superhigh temperature adverse circumstances to improve service life Cause ZrB2Base composite ceramic layer is blocked up, produce the phenomenon for coming off so as to cause stress excessive；Meanwhile, give high-temperature oxidation resistant layer Design and optimization provide bigger and more flexible elastic space.Additionally, for ZrB in the present invention2Base composite ceramic layer, is adopting Al is prepared with reactive sputtering2O3During coating, part top layer is oxidized so as to forming ZrO2From outward appearance to inner essence gradual transition Pre-oxidation layer, the oxide layer main component is ZrO2, with outermost Al2O3Coating similar thermal expansion coefficient, can form good Thermal stress that is thermally matched, producing under releasable hot conditionss, improves the adhesive force between film layer.
4th, the present invention proposes a kind of high temperature film sensor antioxidation composite protective Rotating fields, and which is from bottom to top successively For BN insulating barriers, ZrB2Base composite ceramic layer, Al2O3Coating；For the oxidation resistant protective layer single compared to structure, this resists Oxidation composite armor has multiple antioxidant defense, and service life is longer, and temperature applicable range is higher, wider；Obtaining phase On the premise of with antioxidant effect and service life, the equivalent thickness of the compound anti-oxidation layer can be less；These characteristics, not only Be conducive to some superhigh temperature antioxidation ceramic thin sheet applications, and design to high-temperature oxidation resistant layer and optimize there is provided more Big and more flexible elastic space.
Description of the drawings
Fig. 1 is the structural representation of existing plural layers sensor；
Fig. 2 is a kind of structural representation of the thin film sensor based on antioxidation composite armor of the present invention；
The sectional view of the W-Re thin film sensor based on antioxidation composite armor of the present invention that Fig. 3 is provided for embodiment； Wherein, 1 is Ni based alloy substrates, and 2 is NiCrAlY alloy transition layers, and 3 is thermally grown Al2O3Layer, 4 is Al2O3Insulating barrier, 5 are First BN insulating barriers, 6 is the positive negative thermal electrode of film thermocouple, and 7 is the 2nd BN insulating barriers, and 8 is ZrB2Base composite ceramic layer, 9 are Al2O3Coating, wherein 7,8,9 layers constitute antioxidation composite armor of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, technical scheme is described in detail in detail.
Embodiment
As shown in figure 3, the W-Re thin film sensor based on antioxidation composite armor of the present invention provided for embodiment Sectional view；Ni based alloy substrate 1, NiCrAlY alloy transition layer 2, thermally grown Al are followed successively by from bottom to top2O3Layer 3, Al2O3Insulation The 4, the first BN insulating barriers 5 of layer, the positive negative thermal electrode 6 of W-Re film thermocouple, the 2nd BN insulating barriers 7, ZrB2Base composite ceramic layer 8, Al2O3Coating 9.
The preparation method of the W-Re thin film sensor based on antioxidation composite armor of the present invention that embodiment is provided, specifically Comprise the following steps：
Step 1, the surface treatment of Ni based alloy substrates：First Ni based alloy substrate surfaces are processed by shot blasting, then Ultrasonic cleaning 15min is successively carried out to the surface of alloy substrate using industrial degreaser, acetone, ethanol and deionized water, then is used Nitrogen gun is dried up, and dries residual moisture, using plasma cleaning base plate 5min before plated film；
Step 2, the preparation of NiCrAlY alloy transition layers：The Ni based alloy substrates obtained through step 1 process are placed in back end Vacuum is 5.0 × 10-4In the vacuum environment of Pa, with NiCrAlY alloys as target, argon is sputter gas, and sputtering pressure is 0.4Pa, sputtering power are that the method using d.c. sputtering is by NiCrAlY alloys under conditions of 500W, base reservoir temperature are 450 DEG C It is deposited on through, on the nickel-base alloy substrate after step 1 process, deposited film thickness is about 15 μm；
Step 3, thermally grown Al2O3The preparation of layer：The composite base plate obtained after processing through step 2 is placed in vacuum heat In stove, 5 × 10-4Under the high vacuum environment of Pa and 1000 DEG C of temperature conditionss, analysis aluminum processes 10h；Then, 1000 DEG C of temperature are kept And oxygen is passed through to normal pressure, oxidation processes 6h, cool to room temperature with the furnace, obtain band NiCrAlY transition zones and Al2O3Thermally grown layer Composite base plate；
Step 4, Al2O3The preparation of insulating barrier：By the composite base plate for processing gained through step 3 be placed in back end vacuum for 5 × 10-4The vacuum chamber of Pa, is not less than high-purity Al targets of 99.99wt% as target, O using purity2Mixed gas conduct with Ar Sputter gas, O2Flow-rate ratio with Ar is 1:9, sputtering pressure is 0.3Pa, under conditions of substrate temperature is 400 DEG C, using reaction Sputtering method deposits the Al of about 5 μm of a layer thickness2O3Insulating barrier；Then, vacuum is placed it in for 5.0 × 10-4Pa's Made annealing treatment in vacuum annealing furnace, annealing temperature is 1000 DEG C, annealing temperature retention time is 2h, prepares Al2O3Thickness of insulating layer For 5 μm；
Step 5, the preparation of BN insulating barriers：On the composite base plate obtained after through step 4, it is not less than with purity The BN of 99.99wt% is target, using radio frequency magnetron sputtering method in Al2O3BN insulating barriers are sputtered on insulating barrier；Wherein, Back end vacuum is 5 × 10-4Pa, operating air pressure are 0.6Pa, and sputtering power is 300W, and sputter gas are N2Gaseous mixture with Ar Body, N2Flow-rate ratio with Ar is 2:8, underlayer temperature is 300 DEG C, and substrate bias are 150V, control sputtering time, the first of preparation About 10 μm of BN thickness of insulating layer；
Step 6, the preparation of 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 magnetically controlled DC sputtering and the hard mask version matched with Z-shaped hole slot, by W-Re thermoelectricity Even positive pole is successively deposited on through, on the BN insulating barriers after step 5 process, two kinds of thin-film materials are in measured point with negative pole Overlapped formation node；Wherein, specific process parameter：Back end vacuum 5 × 10-4Pa, operating air pressure 0.4Pa, sputtering power The flow of 150W, sputter gas Ar is 25sccm, controls the parameters such as sputtering time, prepares the thickness of W-Re film thermocouple both positive and negative polarity About 2 μm of degree；
Step 7, the preparation of the 2nd BN insulating barriers：The composite base plate with W-Re film thermocouple obtained after through step 6 On, the BN of 99.99wt% is not less than as target with purity, the method using rf magnetron sputtering is in Wolfram rhenium heat electric couple functional layer The 2nd BN insulating barriers are sputtered, and covers Wolfram rhenium heat electric couple functional layer；Wherein, back end vacuum is 5 × 10-4Pa, operating air pressure is 0.6Pa, sputtering power are 300W, and sputter gas are N2With the mixed gas of Ar, N2Flow-rate ratio with Ar is 2:8, underlayer temperature is 300 DEG C, substrate bias are 150V, prepare about 10 μm of the thickness of the 2nd BN insulating barriers；
Step 8, ZrB2The preparation of base composite ceramic layer：On the 2nd BN insulating barriers of step 7 deposition, using radio frequency magnetron Sputtering method deposits Zr-B-Si-C thin film；Wherein, back end vacuum is 5 × 10-4Pa, operating air pressure is 0.6Pa, sputter gas For Ar, Ar flows are 25sccm, and sputtering power is 500W, and underlayer temperature is 400 DEG C, and substrate bias are 150V, the Zr-B- of preparation The thickness of Si-C thin film is 30 μm；The ZrB that the target for adopting is inlayed for SiC2Circular composite target material, ZrB in target2Quality hundred Fraction is 82wt%～88wt%, and the mass percent of SiC is 12wt%～18wt%, or posts silicon chip using symmetrical alternating B with zirconium piece4C targets, B4C, Si and Zr are 10 in the area ratio of sputter area:(2～3):(7～8)；
Step 9, Al2O3The preparation of coating：On the Zr-B-Si-C thin film of step 8 deposition, it is not less than with purity High-purity Al targets of 99.99wt% are target, using the method for reactive sputtering, are 700 DEG C in substrate temperature, and vacuum is 5 × 10- 4O is passed through into vacuum room under conditions of Pa2Mixing sputter gas to air pressure with Ar is 0.4Pa, O2Flow-rate ratio with Ar is 2: 8, prepare the Al for covering Zr-B-Si-C thin film2O3(in the process, the top layer of Zr-B-Si-C thin film can be oxidized, shape for layer Into from outward appearance to inner essence relatively thin ZrO2The pre-oxidation layer of gradient transition, itself and Al2O3Coating similar thermal expansion coefficient, can form good Good is thermally matched, the thermal stress produced under releasable hot conditionss, improves the adhesive force between film layer)；Then it is placed on In vacuum annealing furnace, 5.0 × 10-4Made annealing treatment in the vacuum environment of Pa, annealing temperature is 1000 DEG C, during annealing insulation Between be 2h, you can form thickness about 5 μm of Al on Zr-B-Si-C thin film2O3Coating；It is combined so as to obtain band antioxidation The W-Re film thermocouple structure of overcoat.

Claims (9)

1. a kind of high temperature film sensor antioxidation composite armor, including BN insulating barriers, ZrB2Base composite ceramic layer, Al2O3 Coating, wherein, BN insulating barriers, ZrB2Base composite ceramic layer and Al2O3Coating is sequentially deposited to using evaporation or sputtering method On thin film sensor sensitive function layer.
2. high temperature film sensor antioxidation composite armor according to claim 1, it is characterised 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. high temperature film sensor antioxidation composite armor according to claim 1, it is characterised in that the ZrB2 Base composite ceramic layer is Zr-B-Si-C thin film；Prepared using sputtering method.
4. high temperature film sensor antioxidation composite armor according to claim 1, it is characterised in that the ZrB2 When prepared by base composite ceramic layer, the ZrB that the target for adopting is inlayed for SiC2Composite target material, ZrB in target2Mass percent be The mass percent of 82wt%～88wt%, SiC is 12wt%～18wt%.
5. high temperature film sensor antioxidation composite armor according to claim 1, it is characterised in that the ZrB2 When prepared by base composite ceramic layer, the target for adopting posts the B of silicon chip and zirconium piece for symmetrical alternating4C 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 antioxidation composite armor, comprises the following steps：
Step 1：On the sensitive function layer of thin film sensor, the BN of 99.99wt% is not less than as target with purity, using radio frequency The method sputtering BN insulating barriers of magnetron sputtering；Wherein, back end vacuum is 10-3Below Pa, operating air pressure are 0.2～1.2Pa, splash Power is penetrated for 100～300W, sputter gas are N2With the mixed gas of Ar, underlayer temperature is 100～300 DEG C, and substrate bias are 100V～200V, the thickness for preparing BN insulating barriers are 10～20 μm；
Step 2：On the BN insulating barriers of step 1 deposition, Zr-B-Si-C thin film is deposited using radio frequency magnetron sputtering method；Wherein, Back end vacuum is 10-3Below Pa, operating air pressure are 0.4～1.2Pa, and sputter gas are Ar, and Ar flows are 10～25sccm, splash Power is penetrated for 200～500W, underlayer temperature is 300～500 DEG C, substrate bias are 100～150V, the Zr-B-Si-C of preparation is thin The thickness of film is 20～50 μm；The ZrB that the target for adopting is inlayed for SiC2Composite target material, ZrB in target2Mass percent be The mass percent of 82wt%～88wt%, SiC is 12wt%～18wt%, or posts silicon chip and zirconium piece using symmetrical alternating B4C targets, B4C, Si and Zr are 10 in the area ratio of sputter area:(2～3):(7～8)；
Step 3：On the Zr-B-Si-C thin film of step 2 deposition, high-purity Al targets of 99.99wt% are not less than as target with purity, Using the method for reactive sputtering, substrate temperature be 600～800 DEG C, vacuum be 10-3Under conditions of below Pa into vacuum room 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, prepare and cover The Al of lid Zr-B-Si-C thin film2O3Layer；Then it is placed in vacuum annealing furnace, 10-3Enter in the vacuum environment of below Pa Row annealing, annealing temperature are 1000～1200 DEG C, and annealing temperature retention time is 2～5h, you can shape on Zr-B-Si-C thin film Into the Al that thickness is 2～5 μm2O3Coating；So as to obtain thin film sensor.
7. a kind of high temperature film sensor based on antioxidation composite armor described in claim 1, is followed successively by conjunction from bottom to top Gold base, NiCrAlY alloy transition layers, thermally grown Al2O3Layer, Al2O3Insulating barrier, sensitive function layer, BN insulating barriers, ZrB2Base is multiple Close ceramic layer and Al2O3Coating, wherein, BN insulating barriers, ZrB2Base composite ceramic layer and Al2O3Coating using evaporation or is sputtered Method is sequentially deposited on thin film sensor sensitive function layer.
8. high temperature film sensor according to claim 7, it is characterised in that the Al2O3Insulating barrier and sensitive function layer Between arrange one layer of BN insulating barrier.
9. a kind of preparation method of the high temperature film sensor based on antioxidation composite armor described in claim 1, including with Lower step：
Step 1, the surface treatment of Ni based alloy substrates：First Ni based alloy substrate surfaces are processed by shot blasting, are then adopted Industrial degreaser, acetone, ethanol and deionized water are successively cleaned by ultrasonic to the surface of alloy substrate, then are blown with nitrogen gun Dry, dry residual moisture, using plasma cleaning base plate before plated film；
Step 2, the preparation of NiCrAlY alloy transition layers：The Ni based alloy substrates obtained through step 1 process are placed in back end vacuum Spend for 10-3In the vacuum environment of below Pa, with NiCrAlY alloys as target, argon is sputter gas, sputtering pressure is 0.2～ 1.0Pa, sputtering power be 300～500W, base reservoir temperature be 400～500 DEG C under conditions of, using d.c. sputtering method will On nickel-base alloy substrate of the NiCrAlY alloy depositions after through step 1 process, deposited film thickness is 10～20 μm；
Step 3, thermally grown Al2O3The preparation of layer：The composite base plate obtained after processing through step 2 is placed in vacuum heat treatment furnace, It is higher than 5 × 10 in vacuum-4Under the vacuum environment of Pa and 1000～1200 DEG C of temperature conditionss, analysis aluminum processes 6～10h；Then, protect Hold 1000～1200 DEG C of temperature and oxygen is passed through to normal pressure, 5～10h of oxidation processes, cool to room temperature with the furnace, obtain band NiCrAlY transition zones and Al2O3The composite base plate of thermally grown layer；
Step 4, Al2O3The preparation of insulating barrier：The composite base plate for processing gained through step 3 is placed in back end vacuum for 10-3Pa with Under vacuum chamber, substrate temperature be 200～600 DEG C under conditions of, using evaporation or sputtering method depositing Al2O3Insulating barrier；So Afterwards, place it in vacuum annealing furnace and made annealing treatment, annealing temperature is 1000～1200 DEG C, annealing temperature retention time is 2 ～5h, prepares Al2O3Thickness of insulating layer is 5～10 μm；
Step 5, the preparation of BN insulating barriers：On the composite base plate obtained after through step 4, it is not less than with purity The BN of 99.99wt% is target, using radio frequency magnetron sputtering method in Al2O3BN insulating barriers are sputtered on insulating barrier；Wherein, Back end vacuum is 10-3Below Pa, operating air pressure are 0.2～1.2Pa, and sputtering power is 100～300W, and sputter gas are N2With The mixed gas of Ar, underlayer temperature be 100～300 DEG C, substrate bias be 100V～200V, a BN thickness of insulating layer of preparation 5～20 μm；
Step 6, the preparation of thin film sensor sensitive function layer：The composite base plate that step 5 is obtained is placed in vacuum cavity, is adopted The method of evaporation or sputtering prepares thin film sensor sensitive function layer on BN insulating barriers；
Step 7, the preparation of the 2nd BN insulating barriers：On the composite base plate with sensitive function layer obtained after through step 6, with purity The BN for being not less than 99.99wt% is target, sputters the 2nd BN insulating barriers using the method for rf magnetron sputtering；Wherein, back end is true Reciprocal of duty cycle is 10-3Below Pa, operating air pressure are 0.2～1.2Pa, and sputtering power is 100～300W, and sputter gas are N2Mixed with Ar Close gas, underlayer temperature be 100～300 DEG C, substrate bias be 100V～200V, prepare the 2nd BN insulating barriers thickness be 10～ 20μm；
Step 8, ZrB2The preparation of base composite ceramic layer：On the 2nd BN insulating barriers of step 7 deposition, using rf magnetron sputtering Method deposits Zr-B-Si-C thin film；Wherein, back end vacuum is 10-3Below Pa, operating air pressure are 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 are 100～150V, the thickness of the Zr-B-Si-C thin film of preparation is 20～50 μm；The ZrB that the target for adopting 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 B for symmetrically alternately posting silicon chip and zirconium piece4C targets, B4C, Si and Zr are 10 in the area ratio of sputter area:(2～3): (7～8)；
Step 9, Al2O3The preparation of coating：On the Zr-B-Si-C thin film of step 8 deposition, 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 be 10-3Below Pa Under conditions of be passed through O into vacuum room2Mixing sputter gas to air pressure with Ar is 0.4～1.2Pa, O2Flow-rate ratio with Ar is 1:9～2:8, prepare the Al for covering Zr-B-Si-C thin film2O3Layer；Then it is placed in vacuum annealing furnace, 10- 3Made annealing treatment in the vacuum environment of below Pa, annealing temperature is 1000～1200 DEG C, annealing temperature retention time is 2～5h, i.e., The Al that thickness is 2～5 μm can be formed on Zr-B-Si-C thin film2O3Coating；So as to obtain the thin film sensor.
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CN115028474A (en) * 2022-05-11 2022-09-09 中北大学 Graphene sensor composite thermal protection structure and preparation thereof
CN115028474B (en) * 2022-05-11 2023-09-08 中北大学 Graphene sensor composite thermal protection structure and preparation thereof

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