CN108359926B - Antioxidant/heat-insulating integrated composite coating, polyimide composite material with composite coating coated on surface and preparation method of polyimide composite material - Google Patents

Antioxidant/heat-insulating integrated composite coating, polyimide composite material with composite coating coated on surface and preparation method of polyimide composite material Download PDF

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CN108359926B
CN108359926B CN201810139668.2A CN201810139668A CN108359926B CN 108359926 B CN108359926 B CN 108359926B CN 201810139668 A CN201810139668 A CN 201810139668A CN 108359926 B CN108359926 B CN 108359926B
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rare earth
powder
coating
temperature
composite
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CN108359926A (en
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黄文质
刘海韬
甘霞云
黄丽华
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National University of Defense Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

The invention discloses an antioxidant/heat-insulating integrated composite coating which is of a multilayer stacked structure and sequentially comprises a metal transition layer, a rare earth silicate layer and a rare earth zirconate layer from inside to outside. The invention also provides a polyimide composite material with the surface coated with the composite coating, which comprises a fiber reinforced polyimide resin-based composite material and the composite coating coated on the surface of the fiber reinforced polyimide resin-based composite material, wherein the composite coating is the antioxidant/heat-insulating integrated composite coating. The invention also provides a preparation method of the polyimide composite material with the surface coated with the composite coating. The invention adopts the oxygen-isolating/anti-oxidation integrated coating, can effectively improve the long-term high-temperature oxidation resistance and the short-term high-temperature ablation resistance of the polyimide composite material with the surface coated with the composite coating, thereby widening the application range of the polyimide composite material with the surface coated with the composite coating in aviation and aerospace aircrafts.

Description

Antioxygen/heat-insulation integrative composite coating, the polyimides of surface coating composite coating are multiple Condensation material and preparation method thereof
Technical field
The invention belongs to the modified fields of surface covering more particularly to a kind of composite coating and surface to coat the poly- of composite coating Acid imide composite material and preparation method.
Background technique
Polyimide resin based composites (Polyimide matrix composites, PiMCs) are current heatproofs etc. A kind of highest polymer matrix composites of grade, because it is low with density, fatigue crack-resistant performance is good, corrosion-resistant, specific strength with than The advantages that rigidity is high and performance can design and be used to substitute part metals material.However as aerospace flight vehicle The continuous improvement of flying speed, the performances such as the heat-resisting quantity and wearability of polymer matrix composites are no longer satisfied practical application Demand needs to improve its high temperature resistance.
Compared to new fire resistant resin based composites are developed, it is improved using protective coating technique appropriate and uses temperature The advantages that degree or wearability are most economical, one of the most effective ways, are provided simultaneously on pneumatic design and original shape without influencing. Usual polymer matrix composites aoxidize or decomposes in a high temperauture environment the oxygen being attributable in polymer matrix composites spread and The collective effect of thermal diffusion.Therefore a kind of composite coating with oxygen barrier property and heat-proof quality is developed and with composite coating Polymer matrix composites have a vast market foreground.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, one kind is provided Have the excellent oxygen barrier property antioxygen/heat-insulation integrative composite coating good with heat-proof quality, high-temperature oxidation resistance, and accordingly mentions Above-mentioned antioxygen/heat-insulation integrative composite coating composite polyimide material is coated for surface, and preparation method is accordingly provided. In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of antioxygen/heat-insulation integrative composite coating, the composite coating be multiple-layer stacked structure, the composite coating by It is interior to outside successively include intermediate metal, rare earth silicate layer and rare earth zirconate layer.
In above-mentioned antioxygen/heat-insulation integrative composite coating, it is preferred that the metal in the intermediate metal is aluminium, zinc, tin And its one of alloy, the intermediate metal with a thickness of 0.03~0.15mm.Metal in intermediate metal is generally Low-melting-point metal, influence when can reduce metal deposit to basal layer, thickness data is obtained by optimum experimental, if intermediate The thickness of intermediate metal is too thin, and metal layer is not continuous enough, and the deposition on outer layer rare earth silicate surface layer is easy to cause substrate damage； Thickness too thick coating thermal shock resistance is poor, is easy to appear in Thermal Cycling floating coat and falls off or crack.
In above-mentioned antioxygen/heat-insulation integrative composite coating, it is preferred that the material of the rare earth silicate layer is with excellent One of silicic acid erbium, yttrium silicate and ytterbium silicate of oxygen barrier property, the rare earth silicate layer with a thickness of 0.05~0.15mm； The material of the rare earth zirconate layer is with one of lower thermal conductivity zirconic acid lanthanum, zirconic acid neodymium and cerium acid cerium, the rare earth zirconium Silicate layer with a thickness of 0.05~0.20mm.Rare earth silicate layer and the thickness of rare earth zirconate layer are too thin, and coating is anti-oxidant, anti- Hot property is poor；Too thick coating thermal shock resistance is poor, is easy to appear and falls off or crackle in Thermal Cycling.
As a general technical idea, the present invention also provides a kind of polyimides composite woods of surface coating composite coating Material, the composite coating including composite polyimide material substrate and coated on the composite polyimide material substrate surface, The composite polyimide material substrate is that fiber (preferably quartz fibre) enhances polyimide resin based composites, described multiple Conjunction coating is above-mentioned antioxygen/heat-insulation integrative composite coating.
As a general technical idea, the present invention also provides a kind of polyimides of above-mentioned surface coating composite coating is multiple The preparation method of condensation material, comprising the following steps:
(1) rare earth silicate dusty spray and rare earth zirconate hot spray powder are prepared；
(2) roughening treatment is carried out to composite polyimide material substrate surface, roughening substrate is dried to obtain after cleaning；
(3) it is roughened substrate surface obtained in step (2) using supersonic flame technique and deposits one layer of intermediate metal Obtain substrate containing intermediate metal；
(4) rare earth silicon is sprayed using plasma spray coating process substrate surface containing intermediate metal obtained in step (3) Silicate layer obtains containing rare earth silicate layer substrate；
(5) rare earth is sprayed using plasma spray coating process containing rare earth silicate layer substrate surface obtained in step (4) Zirconic acid salt deposit obtains the composite polyimide material of surface coating composite coating.
In above-mentioned preparation method, it is preferred that prepare the specific preparation of rare earth silicate hot spray powder in the step (1) Method is the following steps are included: by rare earth silicon is obtained using high temperature process heat after rare earth oxide and silica high-temperature heat treatment Silicate material, then rare earth silicate material and water, organic bond, defoaming agent are mixed to form rare earth silicic acid using ball-milling technology Salt ceramic slurry sieves to obtain rare earth silicate hot spray powder again after finally drying using atomizer；The step (1) The middle specific preparation method for preparing rare earth zirconate hot spray powder is the following steps are included: high by rare earth oxide and zirconium dioxide Rare earth zirconate material is obtained using high temperature process heat after warm processing, then by rare earth zirconate material and water, organic bonding Agent, defoaming agent are mixed to form rare earth zirconate ceramic slurry using ball-milling technology, sieve again after finally utilizing atomizer dry Get rare earth zirconate hot spray powder.High-temperature heat treatment can remove the impurity in raw material.
In above-mentioned preparation method, it is preferred that when preparing rare earth silicate hot spray powder in the step (1): the height The temperature of warm processing is 1000~1400 DEG C, and the time is 2~12h；The temperature of the high temperature process heat is 1300~1600 DEG C, the time is 12~40h；The ball-milling technology is to mix on horizontal ball mill, and the velocity of rotation of the horizontal ball mill is 300r/min~800r/min, mixing time are 12~48h；The dry inlet temperature of the atomizer is 200~300 DEG C, outlet temperature is 120~160 DEG C, and slurry flow is 20~65L/min, 15000~23000r/ of atomizer rotation speed min；The screening is sieves using 100~400 mesh standard sieves to the powder particle after drying, to obtain partial size as 37 μm ~150 μm of rare earth silicate hot spray powder；When preparing rare earth zirconate hot spray powder in the step (1): the height The temperature of warm processing is 800~1200 DEG C, and the time is 2~12h；The temperature of the high temperature process heat is 1300~1600 DEG C, the time is 12~40h；The ball-milling technology is to mix on horizontal ball mill, and the velocity of rotation of the horizontal ball mill is 300r/min~800r/min, mixing time are 12~48h；The dry inlet temperature of the atomizer is 200~300 DEG C, outlet temperature is 120~180 DEG C, and slurry flow is 20~60L/min, 12000~20000r/ of atomizer rotation speed min；The screening is sieves using 100~200 mesh standard sieves to the powder particle after drying, to obtain partial size as 74 μm ~150 μm of rare earth zirconate hot spray powder.Above-mentioned atomizer drying process can get the lesser thermal jet of powder diameter Powder is applied, to improve molten state of the powder in Plasma Spraying Process Using, to improve the densification degree of coating, improves and applies Layer antioxygenic property.
In above-mentioned preparation method, it is preferred that the mass fraction of rare earth silicate is in the rare earth silicate ceramic slurry 40~65%, the organic bond is polyethyleneimine, and the mass fraction of the polyethyleneimine is 1~5%, described to disappear Infusion is polyethylene glycol, and the mass fraction of the polyethylene glycol is 0.3~3%, and surplus is water；The rare earth zirconate ceramics The mass fraction of rare earth zirconate is 60~75% in slurry, and the organic bond is Arabic gum, and the Arabic gum Mass fraction be 0.5~5%, the defoaming agent be Triammonium citrate, and the mass fraction of the Triammonium citrate be 0.5~ 4%, surplus is water.Organic bond and antifoam content be excessively high, and to will lead to phosphorus content in thermal spray process floating coat excessively high, applies Layer is excessively loose, and Arabic gum content is too low to make prilling powder that can not form uniform spherical particle.
In above-mentioned preparation method, it is preferred that in the step (2), roughening treatment is by composite polyimide material substrate It is placed in sand-blasting machine and carries out blasting treatment, the technological parameter of blasting treatment are as follows: pressure is 0.1~0.4MPa, and sandblasting distance is 50 ~150mm, sand partial size are 20~70 μm, and blast time is 1~5min；When dry after cleaning, drying temperature is 80~150 ℃。
In above-mentioned preparation method, it is preferred that the technological parameter of the supersonic flame spraying technique is as follows: propane flow is 50~250L/min, O2Throughput is 150~600L/min, 140~380L/min of air mass flow；Powder feeding air-flow N2For 10~ 55L/min, 30~100g/min of powder sending quantity；Spray distance is 180~400mm；Plasma spray coating process in the step (4) Technological parameter are as follows: Ar throughput be 20~40L/min, H2Throughput is 6~12L/min；Powder feeding air-flow Ar be 1.5~ 3.5L/min, powder sending quantity 20%~60%；Size of current control is 520~580A, and power is 30~36kW；Spray distance is 80 ~150mm；The technological parameter of plasma spray coating process in the step (5) are as follows: Ar throughput is 35~45L/min, H2Gas Flow is 6~15L/min；Powder feeding air-flow Ar is 2.3~4.5L/min, powder sending quantity 15%~50%；Size of current control is 550 ~650A, power are 35~45kW；Spray distance is 80~180mm.
It is smaller can to prepare powder diameter by the preparation of optimization rare earth silicate slurry and drying process with atomizing by the present invention And the uniform powder particle of distribution, be conducive to the molten state for improving powder in spraying process, improve rare earth silicate and apply The densification degree of layer；Meanwhile present invention optimizes rare earth zirconate spray-dried techniques, regulate and control rare earth zirconate powder Particle size, improves the mobility and its dimensional homogeneity of rare earth zirconate hot spray powder, thus effectively increase etc. from The densification degree of sub- spray-on coating reduces oxygen diffusion admittance；In addition, present invention optimizes intermediate metals and rare earth zirconic acid Salt spraying process reduces the destruction in spraying process to resin matrix surface.
In the present invention by fiber reinforced polyimide polymer matrix composites surface deposition have good heat resistance energy, Heat-insulated and antioxygenic property ceramic protection coating system, can significantly improve fiber reinforced polyimide polymer matrix composites Long-term oxidation resistance energy, heat resistanceheat resistant performance and used life.Rare earth zirconate ceramic material has lower thermal conductivity, wear-resistant, resistance to The excellent properties such as high temperature, corrosion-resistant and resistance to oxidation are supported on fiber reinforced polyimide polymer matrix composites surface, energy Conduction of heat is effectively reduced；Meanwhile have in rare earth zirconate lattice 1/8 oxygen case hole, in high ion doping concentration Under, superfluous Lacking oxygen forms clustering architecture, and leading to it at high temperature has lower oxygen ionic conductivity, to realize heat-insulated With oxygen barrier function, it is remarkably improved the high-temperature oxidation resistance of composite material.In addition, multiple in fiber reinforced polyimide resin base There is one layer of low-melting-point metal layer between condensation material and ceramic protection coating, it can be to avoid plasma spraying high-melting-point ceramic material pair The destruction on fiber reinforced polyimide polymer matrix composites surface, to improve coating and fiber reinforced polyimide resin base Interface cohesion between composite material.Compared to electric arc spraying and plasma spraying, using supersonic flame spraying metal layer knot It is low to close intensity height, porosity, and coating is in compression, is conducive to improve coating high-temp thermal shock resistance；And flame temperature compared with Low, the influence to fiber reinforced polyimide polymer matrix composites surface is smaller.
In preparation technology of coating, have that preparation process is flexible, high-efficient, sprayed on material model using plasma spray coating process Enclose wide, coating layer thickness is easy to control, process stabilizing and it is reproducible the advantages that, be suitable for depositing dystectic ceramic coating.But by It is higher in rare earth zirconate coating material fusing point, the porosity of plasma spraying rare earth zirconate coating between 10~20%, And these holes can become the oxygen diffusion admittance in coating, reduce the oxygen barrier effect of rare earth zirconate coating.In contrast, dilute Native silicate material fusing point is lower, and because having excellent oxygen barrier property, it is coated on intermediate metal and rare earth zirconate layer Between can preferably play the role of oxygen-impermeable, improve the high-temperature oxidation resistance of composite material.
Compared with the prior art, the advantages of the present invention are as follows:
1, it is high to improve fiber reinforced polyimide polymer matrix composites using surface oxidation-resistant coating technology by the present invention Warm antioxygenic property can solve to improve composite material high-temperature oxidation resistance by resin modified with key monomers synthesis again Miscellaneous, the problems such as cure process problem is big, at high cost.The present invention is directed to the aerobic use environment of high temperature, the rare earth silicic acid of design Salt and rare earth zirconate double-layer structure coating are provided simultaneously with oxygen barrier and heat insulating function, advantageously reduce fiber reinforced polyimide tree Oxygen diffusion and heat transfer in resin-based composite, can effectively improve fiber reinforced polyimide polymer matrix composites it is long when it is anti- High temperature oxidation resistance uses model in Aeronautics and Astronautics aircraft to widen fiber reinforced polyimide polymer matrix composites It encloses, is conducive to it in the popularization of field of aerospace.
2, the present invention has one layer of low melting point gold in fiber reinforced polyimide polymer matrix composites and ceramic protection coating Belong to layer, fiber reinforced polyimide polymer matrix composites surface can be broken to avoid plasma spraying high-melting-point ceramic material It is bad, to improve the interface cohesion between coating and fiber reinforced polyimide polymer matrix composites.
3, flame temperature is low when the present invention uses supersonic flame spraying intermediate metal, can effectively reduce to fiber reinforcement The damage on polyimide resin based composites surface；Simultaneously as the flying speed of supersonic flame spraying powder particle is fast, The metal layer of preparation has many advantages, such as that bond strength is high, porosity is low, coating is in compression.
4, the present invention has processing performance using mature supersonic flame spraying and plasma spray coating process prepares coating Stablize, coating heterogeneous microstructure controllability is strong, can reduce coating porosity and microdefect, improves the anti-oxidant anti-of coating Hot property.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention Some embodiments for those of ordinary skill in the art without creative efforts, can also basis These attached drawings obtain other attached drawings.
Fig. 1 is the structural schematic diagram for the composite polyimide material that surface of the present invention coats composite coating.
Fig. 2 be embodiment 1 prepare coated powder XRD diagram (a is Er in figure2SiO5, b La2Zr2O7)。
Fig. 3 is coated powder microscopic appearance figure (a, b La in figure prepared by embodiment 12Zr2O7, c, d are in figure Er2SiO5)。
Fig. 4 is Al/Er prepared by embodiment 12SiO5/La2Zr2O7Coating cross sections microscopic appearance figure.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
As shown in Figure 1, a kind of composite polyimide material of surface coating composite coating, including composite polyimide material Substrate and composite coating coated on the composite polyimide material substrate surface.Composite polyimide material substrate is stone English fiber reinforced polyimide polymer matrix composites, composite coating are that antioxygen/heat-insulation integrative of three layers of overlaying structure is compound Coating is followed successively by metal Al transition zone, Er since composite polyimide material substrate surface2SiO5For ceramic inner layer with La2Zr2O7Top ceramic layer.Wherein, metal Al layer is with a thickness of 31 μm, Er2SiO5With a thickness of 70 μm, La2Zr2O7With a thickness of 50 μm.
In the present embodiment surface coating composite coating composite polyimide material preparation method the following steps are included:
(1) raw material high-temperature heat treatment: erbium oxide and silica material powder are placed in high temperature box furnace at heat Reason controls technological parameter are as follows: heat treatment temperature is 1200 DEG C, soaking time 6h；
(2)Er2SiO5Synthesis: the erbium oxide and silica after being heat-treated so that step (1) is middle is raw materials, using height Warm synthesis in solid state prepares Er2SiO5Material controls technological parameter are as follows: high temperature process heat temperature is 1500 DEG C, and soaking time is 24h；
(3)Er2SiO5Slurry preparation: the Er that step (2) are synthesized2SiO5, deionized water, polyethyleneimine and poly- second two Alcohol mixing, prepares Er by ball-milling technology2SiO5Ceramic slurry controls technological parameter are as follows: Er2SiO5Mass fraction be 55%, the mass fraction of polyethyleneimine is 1.5%, and the mass fraction of polyethylene glycol is 0.5%, and surplus is water；Horizontal ball milling Machine revolving speed is 600r/min, and mixing time is for 24 hours；
(4) atomizer is dry: being used for the Er with certain fluidity of thermal spraying in order to obtain2SiO5Powder uses The Er that atomizer drying process synthesizes step (3)2SiO5Ceramic slurry is dry, to obtain spherical Er2SiO5Reunite Particle controls technological parameter are as follows: inlet temperature is 250 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry flow For 40L/min, centrifugal type atomizer rotation speed is 20000r/min；Using the standard screen of 200 mesh numbers and 400 mesh numbers to drying Powder afterwards is sieved, and the Er that powder diameter is 35~75 μm is obtained2SiO5Powder；
(5) raw material high-temperature heat treatment: lanthanum sesquioxide and zirconium dioxide raw material powder are placed in high temperature box furnace at heat Reason controls technological parameter are as follows: heat treatment temperature is 1000 DEG C, soaking time 6h；
(6)La2Zr2O7Synthesis: the lanthanum sesquioxide and zirconium dioxide after being heat-treated so that step (5) is middle is raw materials, using height Warm synthesis in solid state prepares La2Zr2O7Material controls technological parameter are as follows: high temperature process heat temperature is 1450 DEG C, and soaking time is 24h；
(7)La2Zr2O7Slurry preparation: the La that step (6) are synthesized2Zr2O7, deionized water, Arabic gum and citric acid three Ammonium mixing, prepares La by ball-milling technology2Zr2O7Ceramic slurry controls technological parameter are as follows: La2Zr2O7Mass fraction be 65%, the mass fraction of Arabic gum is 1.0%, and the mass fraction of Triammonium citrate is 0.8%, and surplus is water；Horizontal ball milling Machine revolving speed is 600r/min, and mixing time is for 24 hours；
(8) atomizer is dry: being used for the La with certain fluidity of thermal spraying in order to obtain2Zr2O7Powder is adopted The La for being synthesized step (7) with atomizer drying process2Zr2O7Ceramic slurry is dry, to obtain spherical La2Zr2O7 Agglomerated particle controls technological parameter are as follows: inlet temperature is 255 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry Flow is 35L/min, and centrifugal type atomizer rotation speed is 17000r/min；Utilize the standard screen pair of 100 mesh numbers and 150 mesh numbers Powder after drying is sieved, and the La that powder diameter is 75~100 μm is obtained2Zr2O7Powder；
(9) matrix blasting craft: roughening treatment is carried out to composite polyimide material substrate surface using blasting craft, is surpassed It is dry after sound cleaning, control technological parameter are as follows: pressure control is 0.15MPa when roughening treatment, and sandblasting distance is 150mm, sand Partial size is 30~50 μm, blast time 2min；Drying temperature is 80 DEG C；
(10) supersonic flame spraying Al layers: being deposited to Al powder in step (9) after roughening using supersonic flame spraying Substrate surface, control technological parameter are as follows: propane flow 180L/min, O2Throughput is 360L/min, air mass flow 230L/ min；Powder feeding air-flow N2For 22L/min, powder sending quantity 45g/min；Spray distance is 260mm；
(11) plasma spraying Er2SiO5Layer: Er will be prepared using plasma spraying in step (4)2SiO5Powder deposits to The Al layer surface of step (10) preparation, controls technological parameter are as follows: Ar throughput is 35L/min, H2Throughput is 8L/min；Powder feeding Air-flow Ar is 1.8L/min, powder sending quantity 30%；Size of current control is 550A, power 33kW；Spray distance is 125mm；
(12) plasma spraying La2Zr2O7Layer: La will be prepared using plasma spraying in step (8)2Zr2O7Powder deposition To the Er of step (11) preparation2SiO5Layer surface controls technological parameter are as follows: Ar throughput is 40L/min, H2Throughput is 12L/ min；Powder feeding air-flow Ar is 2.5L/min, powder sending quantity 35%；Size of current control is 600A, power 40kW；Spray distance For 140mm.
In the present embodiment, distinguished using the silicic acid erbium of high temperature process heat technique preparation and the XRD spectrum of zirconic acid lanthanum powder As shown in Figure 2；The silicic acid erbium powder main component wherein synthesized is Er2SiO5, and zirconic acid lanthanum powdered ingredients are pyrochlore phase La2Zr2O7.The powder microscopic appearance prepared using drying process with atomizing is as shown in Figure 3.In addition, as shown in Figure 4, in the present embodiment Thermal spraying antioxygen/heat-insulation integrative coating structure by Al layers, Er2SiO5Internal layer and La2Zr2O7Outer layer is formed.The present embodiment Preparation containing antioxygen/heat-insulation integrative coating at 450 DEG C, after 40 thermal shocks, coating is complete, without obviously fall off, crackle Phenomena such as, show Al/Er2SiO2/La2Zr2O7Multilayered structure coating has excellent thermal shock resistance at 450 DEG C, has good Good applied at elevated temperature performance.15h is aoxidized under the conditions of 450 DEG C of isoperibols, is coated with Al/Er2SiO2/La2Zr2O7Multilayered structure The quartz fibre enhancing polyimide resin based composites unit area weightlessness of coating can be by 88.7mg/cm2It is down to 5mg/cm2, Excellent high-temperature oxidation resistance is shown, with good application prospect.
Comparative example 1:
The composite polyimide material of the surface coating composite coating of the present embodiment, including composite polyimide material substrate And the composite coating coated on composite polyimide material substrate surface.Composite polyimide material substrate is quartz fibre increasing Strong polyimide resin based composites, composite coating is double-layer structure, since composite polyimide material substrate surface according to Secondary is metal Al intermediate layer, zirconic acid lanthanum top ceramic layer.Wherein, metal Al layer is with a thickness of 31 μm, and zirconic acid lanthanum layer is with a thickness of 200 μm。
In the present embodiment surface coating composite coating composite polyimide material preparation method the following steps are included:
(1) raw material high-temperature heat treatment: being placed in lanthana and zirconia material powder in high temperature box furnace and be heat-treated, control Technological parameter are as follows: heat treatment temperature is 1000 DEG C, soaking time 5h；
(2) zirconic acid lanthanum synthesizes: the lanthana and zirconium oxide after being heat-treated so that step (1) is middle is raw materials, using high temperature solid-state It is synthetically prepared zirconic acid lanthanum material, controls technological parameter are as follows: high temperature process heat temperature is 1400 DEG C, and soaking time is for 24 hours；
(3) prepared by zirconic acid lanthanum slurry: by the zirconic acid lanthanum and deionized water, Arabic gum, Triammonium citrate of step (2) synthesis Mixing prepares zirconic acid lanthanum ceramic slurry by ball-milling technology, controls technological parameter are as follows: and the mass fraction of zirconic acid lanthanum is 60%, The mass fraction of Arabic gum is 1.8%, and the mass fraction of Triammonium citrate is 1.0%；Horizontal ball mill revolving speed is 600r/ Min, mixing time 36h；
(4) atomizer is dry: being used for the zirconic acid lanthanum powder with certain fluidity of thermal spraying in order to obtain, uses The ceramic slurry that atomizer drying process synthesizes step (3) is dry, to obtain spherical zirconic acid lanthanum agglomerated particle, control Technological parameter processed are as follows: inlet temperature is 250 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry flow 50L/ Min, centrifugal type atomizer rotation speed are 19000r/min；
(5) substrate blasting craft: fiber reinforced polyimide polymer matrix composites surface is carried out using blasting craft Roughening treatment, it is dry after ultrasonic cleaning, control technological parameter are as follows: pressure control is 0.20MPa when roughening treatment, and sandblasting distance is 120mm, sand partial size are 30~50 μm, blast time 2min；It is cleaned by ultrasonic 5min；Drying temperature is 100 DEG C；
(6) supersonic flame spraying Al layers: being deposited to Al powder in step (5) after roughening using supersonic flame spraying Substrate surface controls technological parameter are as follows: propane flow 160L/min, O2Throughput is 350L/min, air mass flow 260L/ min；Powder feeding air-flow N2For 20L/min, powder sending quantity 50g/min；Spray distance is 240mm；
(7) plasma spraying zirconic acid lanthanum layer: the zirconic acid lanthanum powder prepared in step (4) is deposited to using plasma spraying The Al layer surface of step (6) preparation, controls technological parameter are as follows: Ar throughput is 40L/min, H2Throughput is 9L/min；Powder feeding Air-flow Ar is 3.0L/min, powder sending quantity 30%；Size of current control is 550A, power 38kW；Spray distance is 135mm.
The Al/ zirconic acid lanthanum double-layer structure for combining supersonic flame spraying and plasma spray coating process to prepare in the present embodiment Average thickness is 255 μm, aoxidizes 15h under the conditions of 450 DEG C of isoperibols, the quartz fibre coated with double-layer structure composite coating Enhancing polyimide resin based composites unit area weightlessness can be by 88.7mg/cm2It is down to 9.3mg/cm2, show it with good Good high-temperature oxidation resistance.The mean thermal expansion coefficients of zirconic acid lanthanum coating are 9.36 × 10-6K-1, this coating is in 450 DEG C of conditions Lower thermal shock cycle life is 32 times.
Comparative example 2:
As shown in Figure 1, a kind of composite polyimide material of surface coating composite coating, including composite polyimide material Substrate and composite coating coated on the composite polyimide material substrate surface.Composite polyimide material substrate is stone English fiber reinforced polyimide polymer matrix composites, composite coating are that antioxygen/heat-insulation integrative of three layers of overlaying structure is compound Coating is followed successively by metal Al transition zone, Er since composite polyimide material substrate surface2SiO5For ceramic inner layer with La2Zr2O7Top ceramic layer.Wherein, metal Al layer is with a thickness of 31 μm, Er2SiO5With a thickness of 70 μm, La2Zr2O7With a thickness of 50 μm.
In the present embodiment surface coating composite coating composite polyimide material preparation method the following steps are included:
(1) raw material high-temperature heat treatment: erbium oxide and silica material powder are placed in high temperature box furnace at heat Reason controls technological parameter are as follows: heat treatment temperature is 1200 DEG C, soaking time 6h；
(2)Er2SiO5Synthesis: the erbium oxide and silica after being heat-treated so that step (1) is middle is raw materials, using height Warm synthesis in solid state prepares Er2SiO5Material controls technological parameter are as follows: high temperature process heat temperature is 1500 DEG C, and soaking time is 24h；
(3)Er2SiO5Slurry preparation: the Er that step (2) are synthesized2SiO5, deionized water, polyethyleneimine and poly- second two Alcohol mixing, prepares Er by ball-milling technology2SiO5Ceramic slurry controls technological parameter are as follows: Er2SiO5Mass fraction be 55%, the mass fraction of polyethyleneimine is 1.5%, and the mass fraction of polyethylene glycol is 0.5%, and surplus is water；Horizontal ball milling Machine revolving speed is 600r/min, and mixing time is for 24 hours；
(4) atomizer is dry: being used for the Er with certain fluidity of thermal spraying in order to obtain2SiO5Powder uses The Er that atomizer drying process synthesizes step (3)2SiO5Ceramic slurry is dry, to obtain spherical Er2SiO5Reunite Particle controls technological parameter are as follows: inlet temperature is 250 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry flow For 40L/min, centrifugal type atomizer rotation speed is 20000r/min；Using the standard screen of 200 mesh numbers and 400 mesh numbers to drying Powder afterwards is sieved, and the Er that powder diameter is 35~75 μm is obtained2SiO5Powder；
(5) raw material high-temperature heat treatment: lanthanum sesquioxide and zirconium dioxide raw material powder are placed in high temperature box furnace at heat Reason controls technological parameter are as follows: heat treatment temperature is 1000 DEG C, soaking time 6h；
(6)La2Zr2O7Synthesis: the lanthanum sesquioxide and zirconium dioxide after being heat-treated so that step (5) is middle is raw materials, using height Warm synthesis in solid state prepares La2Zr2O7Material controls technological parameter are as follows: high temperature process heat temperature is 1450 DEG C, and soaking time is 24h；
(7)La2Zr2O7Slurry preparation: the La that step (6) are synthesized2Zr2O7, deionized water, Arabic gum and citric acid three Ammonium mixing, prepares La by ball-milling technology2Zr2O7Ceramic slurry controls technological parameter are as follows: La2Zr2O7Mass fraction be 65%, the mass fraction of Arabic gum is 1.0%, and the mass fraction of Triammonium citrate is 0.8%, and surplus is water；Horizontal ball milling Machine revolving speed is 600r/min, and mixing time is for 24 hours；
(8) atomizer is dry: being used for the La with certain fluidity of thermal spraying in order to obtain2Zr2O7Powder is adopted The La for being synthesized step (7) with atomizer drying process2Zr2O7Ceramic slurry is dry, to obtain spherical La2Zr2O7 Agglomerated particle controls technological parameter are as follows: inlet temperature is 255 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry Flow is 35L/min, and centrifugal type atomizer rotation speed is 17000r/min；Utilize the standard screen pair of 100 mesh numbers and 150 mesh numbers Powder after drying is sieved, and the La that powder diameter is 75~100 μm is obtained2Zr2O7Powder；
(9) matrix blasting craft: roughening treatment is carried out to composite polyimide material substrate surface using blasting craft, is surpassed It is dry after sound cleaning, control technological parameter are as follows: pressure control is 0.15MPa when roughening treatment, and sandblasting distance is 150mm, sand Partial size is 30~50 μm, blast time 2min；Drying temperature is 80 DEG C；
(10) plasma spraying Al layers: Al powder is deposited to using plasma spray coating process by the base after being roughened in step (9) Bottom surface controls technological parameter are as follows: Ar throughput is 30L/min, H2Throughput is 8L/min；Powder feeding air-flow Ar is 3L/min, Powder sending quantity is 30%；Size of current control is 520A, power 30kW；Spray distance is 120mm；
(11) plasma spraying Er2SiO5Layer: Er will be prepared using plasma spraying in step (4)2SiO5Powder deposits to The Al layer surface of step (10) preparation, controls technological parameter are as follows: Ar throughput is 35L/min, H2Throughput is 8L/min；Powder feeding Air-flow Ar is 1.8L/min, powder sending quantity 30%；Size of current control is 550A, power 33kW；Spray distance is 125mm；
(12) plasma spraying La2Zr2O7Layer: La will be prepared using plasma spraying in step (8)2Zr2O7Powder deposition To the Er of step (11) preparation2SiO5Layer surface controls technological parameter are as follows: Ar throughput is 40L/min, H2Throughput is 12L/ min；Powder feeding air-flow Ar is 2.5L/min, powder sending quantity 35%；Size of current control is 600A, power 40kW；Spray distance For 140mm.
Antioxygen manufactured in the present embodiment/heat-insulation integrative coating is at 450 DEG C, and after 20 thermal shocks, coating surface goes out Phenomena such as existing crackle, side are layered, shows plasma spraying Al/Er2SiO2/La2Zr2O7Multilayered structure composite coating high temperature Service life is decreased obviously, and significantly lower than by Al layers of supersonic flame spraying and plasma spraying Er2SiO2/La2Zr2O7Coating The thermal shock lifetime of composed composite coating.
Embodiment 2:
As shown in Figure 1, a kind of composite polyimide material of surface coating composite coating, including composite polyimide material Substrate and composite coating coated on the composite polyimide material substrate surface.Composite polyimide material substrate is stone English fiber reinforced polyimide polymer matrix composites, composite coating are that antioxygen/heat-insulation integrative of three layers of overlaying structure is compound Coating is followed successively by metal Al transition zone, Yb since composite polyimide material substrate surface2SiO5For ceramic inner layer with Nd2Zr2O7Top ceramic layer.Wherein, metal Al layer is with a thickness of 42 μm, Yb2SiO5With a thickness of 55 μm, Nd2Zr2O7With a thickness of 120 μm.
In the present embodiment surface coating composite coating composite polyimide material the preparation method is as follows:
(1) raw material high-temperature heat treatment: yttria and silica material powder are placed in high temperature box furnace at heat Reason controls technological parameter are as follows: heat treatment temperature is 1200 DEG C, soaking time 6h；
(2)Yb2SiO5Synthesis: the yttria and silica after being heat-treated so that step (1) is middle is raw materials, using height Warm synthesis in solid state prepares Yb2SiO5Material controls technological parameter are as follows: high temperature process heat temperature is 1500 DEG C, and soaking time is 24h；
(3)Yb2SiO5Slurry preparation: the Yb that step (2) are synthesized2SiO5, deionized water, polyethyleneimine and poly- second two Alcohol mixing, prepares Yb by ball-milling technology2SiO5Ceramic slurry controls technological parameter are as follows: Yb2SiO5Mass fraction be 55%, the mass fraction of polyethyleneimine is 1.5%, and the mass fraction of polyethylene glycol is 0.5%, and surplus is water；Horizontal ball milling Machine revolving speed is 600r/min, and mixing time is for 24 hours；
(4) atomizer is dry: being used for the Yb with certain fluidity of thermal spraying in order to obtain2SiO5Powder uses The Yb that atomizer drying process synthesizes step (3)2SiO5Ceramic slurry is dry, to obtain spherical Yb2SiO5Reunite Particle controls technological parameter are as follows: inlet temperature is 250 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry flow For 40L/min, centrifugal type atomizer rotation speed is 20000r/min；Using the standard screen of 200 mesh numbers and 400 mesh numbers to drying Powder afterwards is sieved, and the Yb that powder diameter is 35~75 μm is obtained2SiO5Powder；
(5) raw material high-temperature heat treatment: neodymium oxide and zirconium dioxide raw material powder are placed in high temperature box furnace at heat Reason controls technological parameter are as follows: heat treatment temperature is 1000 DEG C, soaking time 6h；
(6)Nd2Zr2O7Synthesis: the neodymium oxide and zirconium dioxide after being heat-treated so that step (5) is middle is raw materials, using height Warm synthesis in solid state prepares Nd2Zr2O7Material controls technological parameter are as follows: high temperature process heat temperature is 1450 DEG C, and soaking time is 24h；
(7)Nd2Zr2O7Slurry preparation: the Nd that step (6) are synthesized2Zr2O7, deionized water, Arabic gum and citric acid three Ammonium mixing, prepares Nd by ball-milling technology2Zr2O7Ceramic slurry controls technological parameter are as follows: Nd2Zr2O7Mass fraction be 65%, the mass fraction of Arabic gum is 1.0%, and the mass fraction of Triammonium citrate is 0.8%, and surplus is water；Horizontal ball milling Machine revolving speed is 600r/min, and mixing time is for 24 hours；
(8) atomizer is dry: being used for the Nd with certain fluidity of thermal spraying in order to obtain2Zr2O7Powder is adopted The Nd for being synthesized step (7) with atomizer drying process2Zr2O7Ceramic slurry is dry, to obtain spherical Nd2Zr2O7 Agglomerated particle controls technological parameter are as follows: inlet temperature is 255 DEG C when atomizer is dry, and outlet temperature is 125 DEG C, slurry Flow is 35L/min, and centrifugal type atomizer rotation speed is 17000r/min；Utilize the standard screen pair of 100 mesh numbers and 150 mesh numbers Powder after drying is sieved, and the Nd that powder diameter is 75~100 μm is obtained2Zr2O7Powder；
(9) matrix blasting craft: fiber reinforced polyimide polymer matrix composites surface is carried out using blasting craft Roughening treatment, it is dry after ultrasonic cleaning, control technological parameter are as follows: pressure control is 0.15MPa when roughening treatment, and sandblasting distance is 150mm, sand partial size are 30~50 μm, blast time 2min；Drying temperature is 80 DEG C；
(10) supersonic flame spraying Al layers: being deposited to Al powder in step (9) after roughening using supersonic flame spraying Substrate surface, control technological parameter are as follows: propane flow 180L/min, O2Throughput is 360L/min, air mass flow 230L/ min；Powder feeding air-flow N2For 22L/min, powder sending quantity 45g/min；Spray distance is 260mm；
(11) plasma spraying Yb2SiO5Layer: Yb will be prepared using plasma spraying in step (4)2SiO5Powder deposits to The Al layer surface of step (10) preparation, controls technological parameter are as follows: Ar throughput is 35L/min, H2Throughput is 8L/min；Powder feeding Air-flow Ar is 1.8L/min, powder sending quantity 30%；Size of current control is 550A, power 33kW；Spray distance is 125mm；
(12) plasma spraying Nd2Zr2O7Layer: Nd will be prepared using plasma spraying in step (8)2Zr2O7Powder deposition To the Yb of step (11) preparation2SiO5Layer surface controls technological parameter are as follows: Ar throughput is 40L/min, H2Throughput is 12L/ min；Powder feeding air-flow Ar is 2.5L/min, powder sending quantity 35%；Size of current control is 600A, power 40kW；Spray distance For 140mm.
Antioxygen/heat-insulation integrative in the composite polyimide material of coating composite coating in surface manufactured in the present embodiment applies Layer at 450 DEG C, after 55 thermal shocks, coating is complete, without obviously fall off, crackle phenomena such as, show that coating has at 450 DEG C There is excellent thermal shock resistance, with good application prospect.15h is aoxidized under the conditions of 450 DEG C of isoperibols, is coated with Al/ Yb2SiO5/Nd2Zr2O7The quartz fibre enhancing polyimide resin based composites unit area weightlessness of multilayered structure coating can By 88.7mg/cm2It is down to 5.1mg/cm2, excellent high-temperature oxidation resistance is shown, with good application prospect.

Claims (8)

1. a kind of preparation method of the composite polyimide material of surface coating composite coating, the surface coating composite coating Composite polyimide material include composite polyimide material substrate and be coated on the composite polyimide material substrate table The composite coating in face, the composite polyimide material substrate is fiber reinforced polyimide polymer matrix composites, described multiple Close coating successively includes intermediate metal, rare earth silicate layer and rare earth zirconate layer from the inside to the outside, which is characterized in that the system Preparation Method the following steps are included:
(1) rare earth silicate dusty spray and rare earth zirconate hot spray powder are prepared；
(2) roughening treatment is carried out to composite polyimide material substrate surface, roughening substrate is dried to obtain after cleaning；
(3) one layer of intermediate metal is deposited in roughening substrate surface obtained in step (2) using supersonic flame technique to obtain Substrate containing intermediate metal；Wherein, the metal in the intermediate metal is one of aluminium, zinc, tin and its alloy；
(4) rare earth silicate is sprayed using the substrate surface containing intermediate metal that plasma spray coating process obtains in step (3) Layer obtains containing rare earth silicate layer substrate；
(5) rare earth zirconic acid is sprayed using plasma spray coating process containing rare earth silicate layer substrate surface obtained in step (4) Salt deposit obtains the composite polyimide material of surface coating composite coating.
2. preparation method according to claim 1, which is characterized in that the intermediate metal with a thickness of 0.03 ~ 0.15mm。
3. preparation method according to claim 1 or 2, which is characterized in that the material of the rare earth silicate layer is silicic acid One of erbium, yttrium silicate and ytterbium silicate, the rare earth silicate layer with a thickness of 0.05 ~ 0.15mm；The rare earth zirconate The material of layer is one of zirconic acid lanthanum, zirconic acid neodymium and cerium acid cerium, the rare earth zirconate layer with a thickness of 0.05 ~ 0.20mm.
4. preparation method according to claim 1, which is characterized in that prepare rare earth silicate thermal jet in the step (1) The specific preparation method of powder is applied the following steps are included: rare earth oxide is consolidated with after silica high-temperature heat treatment using high temperature It is combined to obtain rare earth silicate material, then rare earth silicate material and water, organic bond, defoaming agent is utilized into ball-milling technology It is mixed to form rare earth silicate ceramic slurry, sieves to obtain rare earth silicate thermal spraying again after finally drying using atomizer Powder；
The specific preparation method of rare earth zirconate hot spray powder is prepared the following steps are included: by rare earth oxygen in the step (1) Rare earth zirconate material is obtained using high temperature process heat after compound and zirconium dioxide high-temperature heat treatment, then by rare earth zirconate material Material is mixed to form rare earth zirconate ceramic slurry using ball-milling technology with water, organic bond, defoaming agent, finally using centrifugal It sieves to obtain rare earth zirconate hot spray powder again after spray drying.
5. the preparation method according to claim 4, which is characterized in that prepare rare earth silicate thermal jet in the step (1) When applying powder: the temperature of the high-temperature heat treatment is 1000~1400 DEG C, and the time is 2~12h；The temperature of the high temperature process heat Degree is 1300~1600 DEG C, and the time is 12~40h；The ball-milling technology is to mix on horizontal ball mill, the horizontal ball milling The velocity of rotation of machine is 300r/min~800r/min, and mixing time is 12~48h；The dry import temperature of the atomizer Degree is 200~300 DEG C, and outlet temperature is 120~160 DEG C, and slurry flow is 20~65L/min, atomizer rotation speed 15000 ~23000r/min；The screening is sieves using 100 ~ 400 mesh standard sieves to the powder particle after drying, to obtain grain The rare earth silicate hot spray powder that diameter is 37 μm ~ 150 μm；
When preparing rare earth zirconate hot spray powder in the step (1): the temperature of the high-temperature heat treatment is 800~1200 DEG C, the time is 2~12h；The temperature of the high temperature process heat is 1300~1600 DEG C, and the time is 12~40h；The ball milling work Skill is to mix on horizontal ball mill, and the velocity of rotation of the horizontal ball mill is 300r/min~800r/min, mixing time For 12~48h；The dry inlet temperature of the atomizer is 200~300 DEG C, and outlet temperature is 120~180 DEG C, slurry Flow is 20~60L/min, 12000~20000r/min of atomizer rotation speed；The screening is to utilize 100 ~ 200 targets standard Sieve sieves the powder particle after drying, to obtain the rare earth zirconate hot spray powder that partial size is 74 μm ~ 150 μm.
6. the preparation method according to claim 4, which is characterized in that rare earth silicic acid in the rare earth silicate ceramic slurry The mass fraction of salt is 40~65%, and the organic bond is polyethyleneimine, and the mass fraction of the polyethyleneimine is 1~5%, the defoaming agent is polyethylene glycol, and the mass fraction of the polyethylene glycol is 0.3~3%, and surplus is water；
In the rare earth zirconate ceramic slurry mass fraction of rare earth zirconate be 60~75%, the organic bond be Ah Primary glue is drawn, and the mass fraction of the Arabic gum is 0.5~5%, the defoaming agent is Triammonium citrate, and the citric acid The mass fraction of three ammoniums is 0.5~4%, and surplus is water.
7. according to claim 1 or preparation method described in any one of 4 ~ 6, which is characterized in that in the step (2), roughening Processing carries out blasting treatment for composite polyimide material substrate to be placed in sand-blasting machine, the technological parameter of blasting treatment are as follows: pressure Power is 0.1~0.4MPa, and sandblasting distance is 50~150mm, and sand partial size is 20~70 μm, and blast time is 1~5min；Cleaning When drying afterwards, drying temperature is 80~150 DEG C.
8. according to claim 1 or preparation method described in any one of 4 ~ 6, which is characterized in that the supersonic flame spraying The technological parameter of technique are as follows: propane flow is 50~250L/min, O2Throughput be 150~600L/min, air mass flow 140~ 380L/min；Powder feeding air-flow N2For 10~55L/min, 30~100g/min of powder sending quantity；Spray distance is 180~400mm；
The technological parameter of plasma spray coating process in the step (4) are as follows: Ar throughput is 20~40L/min, H2Throughput is 6~12L/min；Powder feeding air-flow Ar is 1.5~3.5L/min, powder sending quantity 20%~60%；Size of current control is 520~580A, Power is 30~36kW；Spray distance is 80~150mm；
The technological parameter of plasma spray coating process in the step (5) are as follows: Ar throughput is 35~45L/min, H2 throughput For 6~15L/min；Powder feeding air-flow Ar is 2.3~4.5L/min, powder sending quantity 15%~50%；Size of current control for 550~ 650A, power are 35~45kW；Spray distance is 80~180mm.
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