CN111304578A - Heat insulation/radar wave absorption integrated composite coating, titanium alloy material with composite coating coated on surface and preparation method of titanium alloy material - Google Patents

Heat insulation/radar wave absorption integrated composite coating, titanium alloy material with composite coating coated on surface and preparation method of titanium alloy material Download PDF

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CN111304578A
CN111304578A CN202010127611.8A CN202010127611A CN111304578A CN 111304578 A CN111304578 A CN 111304578A CN 202010127611 A CN202010127611 A CN 202010127611A CN 111304578 A CN111304578 A CN 111304578A
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temperature
powder
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coating
titanium alloy
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CN111304578B (en
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黄文质
刘海韬
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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
    • C23C4/12—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
    • 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
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • 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

Abstract

The invention relates to the field of high-temperature functional ceramic coating materials, and particularly discloses a titanium alloy surface heat insulation/radar wave absorption integrated composite coating which is of a multilayer stacked structure and sequentially comprises a metal bonding layer, a heat insulation ceramic layer, a radar wave absorption layer and an anti-diffusion ceramic layer from inside to outside, wherein the heat insulation ceramic layer is an aluminum oxide-rare earth zirconate composite ceramic layer, and the radar wave absorption layer is a surface-mounted type periodic characteristic arrangement Bi-based composite coating2O3‑SiO2‑B2O3Is a resistance type high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a bonding phase and bismuth ruthenate-Ag as a conductive phase and is used for preventing diffusionThe ceramic layer is a rare earth zirconate layer. The invention also provides a titanium alloy material with the surface coated with the composite coating and a preparation method thereof. The composite coating has excellent heat-insulating property and radar wave-absorbing property, and the temperature resistance, high-temperature thermal shock property and high-temperature wave-absorbing property of the titanium alloy substrate are effectively improved.

Description

Heat insulation/radar wave absorption integrated composite coating, titanium alloy material with composite coating coated on surface and preparation method of titanium alloy material
Technical Field
The invention belongs to the field of high-temperature functional ceramic coating materials, and particularly relates to a heat insulation/radar wave absorption integrated composite coating, a titanium alloy material with a composite coating coated on the surface, and a preparation method of the titanium alloy material.
Background
The thermal barrier coating system consists of a metal bonding layer and a ceramic surface layer, wherein the ceramic surface layer has the characteristic of low thermal conductivity and can provide a heat insulation effect for the metal alloy substrate, so that the surface temperature of the titanium alloy substrate is effectively reduced. Generally, the heat insulation effect of the coating is mainly determined by the surface temperature and the coating thickness of the coating, and researches show that the surface temperature of the metal substrate can be reduced by about 4-6 ℃ for every 25.4 mu m increase of the thickness of the ceramic surface layer when the surface temperature is 1200 ℃, and the coating of Thermal Barrier Coatings (TBCs) on the surface of the titanium alloy substrate is one of the main means for rapidly and effectively improving the high temperature resistance and the heat insulation performance of the titanium alloy substrate. Because the electromagnetic scattering characteristic signals of high-temperature parts are obvious, the severe threat of radar guided weapon attack is faced, the electromagnetic scattering characteristic signals of the metal surface in a high-temperature environment can be effectively reduced by adopting the high-temperature radar wave-absorbing coating, so that the radar echo power is reduced, and the high-temperature radar stealth function ZL201110053460.7 Chinese patent, ZL201110052115.1 Chinese patent, ZL201210139046.2 Chinese patent, ZL201410128311.6 Chinese patent and ZL201610479707.4 Chinese patent documents respectively disclose a plurality of structural wave-absorbing materials based on ceramic matrix composite materials. The surface coating technology has the advantages of simple process technology, small influence on the appearance, no limitation by the shape of a workpiece, low cost, high reliability and the like, and the high-temperature radar wave-absorbing coating is adopted on the high-temperature part of the titanium alloy, so that the electromagnetic scattering characteristic signal intensity of the titanium alloy can be effectively reduced, and the surface coating technology has wide application prospect in the field of high-temperature radar stealth materials.
The traditional high-temperature radar wave-absorbing coating adopts a scheme of adding a radar absorbent into a ceramic coating, on one hand, in order to realize better radar wave-absorbing performance, the addition amount of the radar absorbent is more generally, so that the thermal expansion characteristic and the mechanical property of the coating are greatly changed, and the thermal shock resistance of the coating is obviously reduced; on the other hand, the thermal conductivity of the composite coating is obviously improved due to the excessive content of the added radar absorbent, which is not beneficial to the heat insulation performance of the coating. In addition, due to the large thickness of the coating, the coating is easy to delaminate or fall off in the actual service process, and the above problems are the bottleneck problems that researchers in the field need to solve. 201710943403.3 discloses a high temperature resistant radar infrared compatible stealth coating and a preparation method thereof, relatively speaking, the coating has large thickness, large surface density and further improved thermal shock resistance, and has a certain gap from the practical application requirement. In order to meet the application requirement of integration of the heat-insulating property of the coating and the radar wave-absorbing function, the patent discloses a heat-insulating/radar wave-absorbing integrated composite coating with excellent high temperature resistance and thermal shock resistance, a titanium alloy material with the composite coating coated on the surface and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a heat insulation/radar wave absorption integrated composite coating with excellent high temperature resistance, heat insulation performance and thermal shock resistance, and correspondingly provides a titanium alloy material coated with the composite coating on the surface and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is that the heat insulation/radar wave absorption integrated composite coating is of a multilayer stacked structure, the composite coating sequentially comprises a metal bonding layer, a heat insulation ceramic layer, a radar wave absorption layer and an anti-diffusion ceramic layer from inside to outside, the heat insulation ceramic layer is an alumina-rare earth zirconate composite ceramic layer, and the radar wave absorption layer is a surface mount type periodic characteristic arrangement Bi-based2O3-SiO2-B2O3The high-temperature electromagnetic periodic structure is a resistance type high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a bonding phase and bismuth ruthenate-Ag as a conductive phase, and the anti-diffusion ceramic layer is a rare earth zirconate layer.
The technical scheme of the invention is mainly based on the following principle: the invention firstly utilizes the added alumina to improve the high-temperature electrical property and the micro-mechanical property of the composite ceramic coating, provides a wide electrical property design space for the optimization design of a resistance type high-temperature electromagnetic periodic structure layer, and improves the high-temperature thermal shock resistance and the actual service performance of the coating; secondly, a material system, a periodic structure unit and the size of the periodic structure unit, which are easy to regulate and control, of the high-temperature electromagnetic periodic structure are utilized, so that the strong absorption of the coating on radar waves in a wider frequency band or a specific frequency band can be realized; and finally, coating an anti-diffusion ceramic layer on the resistance type high-temperature electromagnetic periodic structure layer, fixing the material and the pattern of the resistance type high-temperature electromagnetic periodic structure layer by using the sprayed ceramic layer, effectively preventing the micro-evolution of the components and the structure of the high-temperature electromagnetic periodic structure layer or the change of the size of the periodic structure pattern, solving the problem of the radar wave-absorbing performance attenuation of the coating due to the fact that the electrical property of the resistance type high-temperature electromagnetic periodic structure layer is prolonged along with the high-temperature service time, and effectively improving the stability of the long-term high-temperature radar wave-absorbing performance of the.
Preferably, in the heat insulation/radar wave absorption integrated composite coating, the thickness of the metal bonding layer is 0.03-0.08 mm; the thickness of the heat-insulating ceramic layer is 0.70 mm-0.95 mm; the thickness of the radar wave absorbing layer is 0.01 mm-0.03 mm; the thickness of the anti-diffusion ceramic layer is 0.03 mm-0.14 mm.
Preferably, in the heat insulation/radar wave absorption integrated composite coating, the metal bonding layer is a NiCrAlY, CoCrAlY or CoNiCrAlY layer; in the alumina-rare earth zirconate composite ceramic layer, the mass ratio of alumina to rare earth zirconate is 2: 98-20: 80, and the rare earth zirconate is lanthanum zirconate, gadolinium zirconate or samarium zirconate.
Preferably, in the heat insulation/radar wave absorption integrated composite coating, the mass of the conductive phase in the resistance type high-temperature electromagnetic periodic structure layer accounts for 40-70% of the total mass of the conductive phase and the binder phase, and the mass ratio of bismuth ruthenate to Ag in the conductive phase is (50-90): (10-50).
Preferably, in the heat insulation/radar wave absorption integrated composite coating, the periodic dimension a of the resistance type high-temperature electromagnetic periodic structure layer is 5-45 mm.
As a general technical concept, the invention also provides a titanium alloy material with the surface coated with the composite coating, which comprises a titanium alloy substrate and the composite coating coated on the surface of the titanium alloy substrate, wherein the composite coating is the heat insulation/radar wave absorption integrated composite coating.
As a general technical concept, the invention also provides a preparation method of the titanium alloy material with the surface coated with the composite coating, which comprises the following steps:
(1) roughening the surface of the titanium alloy substrate;
(2) preparing a metal bonding layer on the titanium alloy substrate roughened in the step (1) by adopting an atmospheric plasma spraying process;
(3) coating the alumina-rare earth zirconate composite ceramic material on the metal bonding layer obtained in the step (2) by adopting an atmospheric plasma spraying process to obtain a heat-insulating ceramic layer;
(4) coating the high-temperature resistance coating on the heat-insulating ceramic layer in the step (3) by a pattern template-air spraying process, and drying and sintering to obtain a radar wave-absorbing layer;
(5) and (4) preparing an anti-diffusion ceramic layer on the surface of the radar wave absorbing layer in the step (4) by adopting an atmosphere plasma spraying process to obtain the titanium alloy material with the surface coated with the composite coating.
Preferably, in the above preparation method, in the step (1), the roughening treatment is: placing the titanium alloy substrate in a sand blasting machine for sand blasting and coarsening, wherein the sand blasting and coarsening process parameters are as follows: controlling the pressure to be 0.3-0.6 MPa, controlling the sand blasting distance to be 40-150 mm, controlling the sand grain diameter to be 60-120 mu m, and controlling the sand blasting time to be 1-6 min;
in the step (2), the parameters of the atmospheric plasma spraying process are as follows: the flow rate of argon gas is 35-50L/min, and the flow rate of hydrogen gas is 6-12L/min; the current is controlled to be 450-530A, and the power is 28-35 kW; the flow of the powder-feeding argon is 1.0-3.0L/min, and the powder-feeding amount is 15-35%; the spraying distance is 80-150 mm;
in the step (3), the parameters of the atmospheric plasma spraying process are as follows: the flow rate of argon gas is 35-45L/min, and the flow rate of hydrogen gas is 10-15L/min; the current is controlled to be 530-620A, and the power is 30-45 kW; the flow of the powder-feeding argon is 2.0-5.0L/min, and the powder-feeding amount is 5% -35%; the spraying distance is 80-200 mm;
in the step (4), the pressure of air spraying is 0.1-0.6 MPa; the drying temperature is 130-200 ℃, and the drying time is 0.5-5 h; the sintering process parameters are as follows: the peak sintering temperature is 300-600 ℃, the temperature rising speed is 20-25 ℃/min, the sintering time is 10-60 min, and the sintering atmosphere is air;
in the step (5), the parameters of the atmospheric plasma spraying process are as follows: the flow rate of argon gas is 30-45L/min, and the flow rate of hydrogen gas is 7-12L/min; the current is controlled to be 500-600A, and the power is 25-40 kW; the flow of the powder-feeding argon is 1.0-4.0L/min, and the powder-feeding amount is 5% -30%; the spraying distance is 80-200 mm.
Preferably, in the above preparation method, in the step (3), the preparation method of the alumina-rare earth zirconate composite ceramic material comprises the following steps:
①, respectively carrying out high-temperature heat treatment on the rare earth oxide and zirconia raw material powder, sequentially adding the rare earth oxide, zirconia and deionized water into a ball milling tank according to a stoichiometric ratio, and mixing by a wet ball milling process to obtain ceramic slurry;
②, drying the ceramic slurry to obtain dry powder, grinding and refining the dry powder, then screening, and carrying out high-temperature solid-phase synthesis on the screened powder to obtain rare earth zirconate ceramic powder;
③, mixing aluminum oxide powder with the rare earth zirconate ceramic powder obtained in the step ②, sequentially adding deionized water, arabic gum powder and triammonium citrate, uniformly mixing through a ball milling process, and preparing the aluminum oxide-rare earth zirconate composite ceramic material through a spray drying process;
in the step ①, on one hand, in order to reduce the loss of part of zirconia in the ball milling process, and on the other hand, the presence of a small amount of monoclinic phase zirconia is beneficial to improving the fracture toughness of the material, preferably, the heat treatment temperature of the rare earth oxide and the zirconia is 800-1200 ℃, the heat treatment time is 2-12 h, the molar ratio of the rare earth oxide to the zirconia is 1 (2-2.2), and the mass percent of deionized water is 45-60%;
in the step ②, the drying temperature is 60-100 ℃, the drying time is 24-48 h, the high-temperature solid phase synthesis temperature is 1200-1600 ℃, and the reaction time is 12-72 h;
in the step ③, the mass ratio of alumina powder to rare earth zirconate ceramic powder is 2: 98-20: 80, the mass percentage of deionized water is 40-70%, the mass percentage of gum arabic is 0.5-5%, the mass percentage of triammonium citrate is 0.5-5%, the ball milling rotation speed is 250-450 r/min, the stirring time is 48-72 h, and the spray drying process parameters are that the outlet temperature is 100-170 ℃, the inlet temperature is 150-280 ℃, the slurry feeding speed is 0.5-5.0L/min, and the rotation speed of an atomizing disc is 12000-25000 r/min.
Preferably, in the above preparation method, in the step (4), the high-temperature resistance coating is prepared by the following method: uniformly mixing glass raw material powder, smelting at 1200-1500 ℃ for 1-6 h to obtain a glass melt, then pouring the glass melt into deionized water for quenching to obtain glass slag, ball-milling the glass slag into glass powder, uniformly mixing the glass powder with bismuth ruthenate-Ag composite powder to obtain mixed powder, and mixing and grinding the mixed powder with an organic carrier to prepare a high-temperature resistance coating;
the glass raw material powder mainly comprises the following components in percentage by mass: bi2O340％～50％、Re2O35％～9％、Al2O34％～5％、SiO 210％～30％、Li2O 4％～8％、CaO 3％～5％、MgO 1％～5％、B2O33% -6%, Re is rare earth element;
the mixing process of the glass powder and the bismuth ruthenate-Ag composite powder is carried out in a planetary gravity mixer, the revolution speed of the planetary gravity mixer is 1000-1400 rpm, the rotation speed is 20-50% of the revolution speed, and the mixing time is 40-80 min;
mixing and grinding the mixed powder and the organic carrier in a three-roller grinding machine, wherein the rotating speed of the three-roller grinding machine is 200-400 r/min, and the grinding and mixing time is 1-6 h;
the mass percent of the organic carrier in the high-temperature resistance coating is 20-30%, and the organic carrier mainly comprises 75-85% of tributyl citrate, 4-7% of cellulose nitrate and 11-18% of lecithin; the viscosity of the high-temperature resistance coating is 100-250 Pa · s.
Compared with the prior art, the invention has the following beneficial effects:
1. the heat insulation/radar wave absorption integrated composite coating has excellent heat insulation performance, and the problems of broadband wave absorption and thickness reduction (less than or equal to 1.2mm) can be solved by utilizing the electromagnetic multi-resonance effect of the introduced resistance type high-temperature electromagnetic periodic structure layer, so that the temperature resistance, the high-temperature thermal shock performance and the high-temperature wave absorption performance of the titanium alloy substrate are effectively improved.
2. The ceramic thermal insulation layer is added with the alumina to realize the regulation and control of the electrical property of the thermal insulation ceramic layer, an electrical property design space is provided for the structural design of the resistance type high-temperature electromagnetic periodic structure layer, the broadband wave absorption property of the coating is favorably improved, the surface density of the coating can be obviously reduced after the alumina is added, the weight increase of parts caused by the coating is reduced, and the weight is reduced by about 20-30% compared with the existing coating.
3. According to the invention, by utilizing micro cracks generated by mismatching of thermal expansion between the added alumina and the rare earth zirconate main ceramic material and deflection, bifurcation and bridging of weak interfaces thereof on the cracks, the crack expansion path is increased, the main crack expansion energy is consumed, and the crack expansion speed is slowed down, so that the fracture toughness and the strain tolerance of the coating are effectively improved, the micro mechanical parameters of the coating are improved, and the actual thermal shock resistance and the comprehensive service performance of the coating are prolonged.
4. The preparation of the heat insulation/radar wave absorption integrated composite coating adopts a plasma spraying process, and has the advantages of high deposition efficiency, high bonding strength, good thermal shock resistance, high process stability and the like.
5. The invention adopts the pattern template-air spraying process and the heat treatment process to prepare the resistance type high-temperature electromagnetic periodic structure layer, can realize the preparation of the radar wave-absorbing layer on the surface of a complex and special-shaped curved surface member, and has lower cost than the prior art.
6. The preparation method disclosed by the invention is simple in process, relatively mature and easy for large-scale production and application.
Drawings
FIG. 1 is a schematic structural diagram of a titanium alloy material coated with a composite coating on the surface according to the invention.
Fig. 2 is a schematic diagram of a unit structure of the resistive electromagnetic periodic structure layer in embodiment 1 of the present invention.
FIG. 3 is a photograph of a high temperature electrical resistance coating in example 1 of the present invention.
FIG. 4 is a drawing of a titanium alloy substrate surface thermal insulation/radar wave absorption integrated composite coating flat plate sample in example 1 of the present invention.
Fig. 5 is a heat insulation/radar wave absorption integrated composite coating heat insulation curve in embodiment 1 of the present invention.
Fig. 6 is a radar reflectivity curve of the heat insulation/radar wave absorption integrated composite coating in embodiment 1 of the present invention.
Description of the main reference numerals:
the material comprises a titanium alloy substrate 1, a metal bonding layer 2, a heat insulation ceramic layer 3, a radar absorbing layer 4 and an anti-diffusion ceramic layer 5.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Example 1
As shown in fig. 1, a titanium alloy material with a surface coated with a composite coating comprises a titanium alloy substrate and the composite coating coated on the surface of the titanium alloy substrate, wherein the composite coating is a thermal insulation/radar wave absorption integrated composite coating with a quadruple-layer laminated structure, and sequentially comprises a CoCrAlY metal bonding layer, a 3% aluminum oxide-lanthanum zirconate composite thermal insulation ceramic layer, a radar wave absorption layer and a lanthanum zirconate anti-diffusion ceramic layer from inside to outside; the thickness of the metal bonding layer is 0.08mm, the thickness of the 3% aluminum oxide-lanthanum zirconate composite heat-insulating ceramic layer is 0.90mm, the thickness of the radar absorbing layer is 0.02mm, the thickness of the lanthanum zirconate ceramic layer is 0.14mm, and the total thickness of the coating is 1.14 mm. The radar wave-absorbing layer is arranged in a patch type periodic characteristic mannerBi2O3-SiO2-B2O3The resistive high-temperature electromagnetic periodic structure layer is a resistive high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a binder phase and bismuth ruthenate-Ag as a conductive phase, wherein the mass of the conductive phase accounts for 50% of the total mass of the conductive phase and the binder phase, and the mass ratio of the bismuth ruthenate to the Ag in the conductive phase is 70: 30; the periodic dimension a of the resistive high-temperature electromagnetic periodic structure layer is 14.5mm, the side length a.x of the patch is 0.75, and the structure is shown in figure 2.
The preparation method of the titanium alloy material with the surface coated with the composite coating comprises the following steps:
(1) coarsening a titanium alloy substrate: roughening the titanium alloy substrate by adopting a sand blasting process, wherein the sand blasting pressure is controlled to be 0.35MPa, the sand blasting distance is controlled to be 100mm, the sand grain size is 60-100 mu m, and the sand blasting time is 2 min;
(2) spraying a CoCrAlY metal bonding layer on the surface of the titanium alloy substrate in the step (1) by adopting an atmospheric plasma spraying process, wherein the process parameters are as follows: the argon flow is 40L/min, and the hydrogen flow is 8L/min; the current is controlled to be 500A, and the power is 32 kW; the flow of the powder feeding argon gas is 2.0L/min, and the powder feeding amount is 25 percent; the spraying distance is 100 mm;
(3) and (3) spraying an alumina-lanthanum zirconate composite ceramic material on the metal bonding surface obtained in the step (2) by adopting an atmospheric plasma spraying process to obtain a heat-insulating ceramic layer, wherein the process parameters are as follows: the argon flow is 40L/min, and the hydrogen flow is 14L/min; the current is controlled to be 550A, and the power is 40 kW; the flow of the powder-feeding argon gas is 2.0L/min, the powder-feeding amount is 25%, and the spraying distance is 130 mm;
(4) spraying a high-temperature resistance coating on the heat-insulating ceramic layer in the step (3) by adopting a pattern template-air spraying process, and drying and sintering to obtain a resistance type high-temperature electromagnetic periodic structure layer, namely a radar wave-absorbing layer; controlling the pressure to be 0.3MPa in the normal-pressure air spraying process; in the drying process, the drying temperature is controlled to be 160 ℃, and the drying time is 2 hours; the peak sintering temperature is 450 ℃, the heating rate is 20 ℃/min, the sintering time is 40min, and the sintering atmosphere is air;
(5) preparing a lanthanum zirconate ceramic layer on the surface of the radar absorbing layer in the step (4) by adopting an atmosphere plasma spraying process, wherein the process parameters are as follows: the argon flow is 35L/min, and the hydrogen flow is 10.5L/min; the current is controlled to be 550A, and the power is 35 kW; the flow of the powder feeding argon gas is 1.5L/min, and the powder feeding amount is 12.5 percent; the spraying distance was 125 mm.
In the step (3), the preparation method of the 3% alumina-lanthanum zirconate composite ceramic material comprises the following steps:
①, respectively treating the lanthanum oxide and zirconia raw material powder at the high temperature of 1000 ℃ for 8h, sequentially adding a mixture of lanthanum oxide and zirconia with the molar ratio of 1:2.1 and deionized water with the mass percent of 50% into a ball milling tank, and mixing by a wet ball milling process to obtain ceramic slurry;
②, drying the ceramic slurry to obtain dry powder, wherein the drying temperature is 80 ℃, the drying time is 36h, grinding and refining the dry powder, then screening, and carrying out high-temperature solid-phase synthesis on the screened powder in a high-temperature box type furnace to obtain lanthanum zirconate ceramic powder, wherein the high-temperature solid-phase synthesis temperature is 1400 ℃, and the reaction time is 24 h;
③ mixing 3% of alumina powder with 97% of lanthanum zirconate ceramic powder in the step ②, sequentially adding 60% of deionized water, 1.8% of gum arabic and 2.8% of triammonium citrate, uniformly mixing by a ball milling process, wherein the ball milling rotation speed is 400r/min, and the stirring time is 60h, and preparing spheroidal particles with certain fluidity and uniform particle size distribution by a spray drying process, namely the 3% alumina-lanthanum zirconate composite ceramic material, wherein the spray drying process parameters are that the outlet temperature is 125 ℃, the inlet temperature is 230 ℃, the slurry feeding speed is 2.5L/min, and the rotating speed of an atomizing disc is 22000 r/min.
In the step (4), the high-temperature resistance coating is prepared by the following method: uniformly mixing glass raw material powder, smelting at 1400 ℃ for 4h to obtain a glass melt, then pouring the glass melt into deionized water for quenching to obtain glass slag, ball-milling the glass slag into glass powder, and mixing the glass powder with bismuth ruthenate-Ag composite powder to obtain mixed powder; grinding and mixing the mixed powder and the organic carrier to obtain the high-temperature resistance coating as shown in figure 3;
glass raw material powderThe composite material comprises the following components in percentage by mass: bi2O346％、La2O38％、Al2O34.5％、SiO223％、Li2O 6％、CaO 4.5％、MgO 3％、B2O35％；
Mixing the glass powder and the bismuth ruthenate-Ag composite powder in a planetary gravity mixer, wherein the revolution speed of the planetary gravity mixer is 1200rpm, the rotation speed is 45 percent of the revolution speed, and the mixing time is 45 min; the grinding and mixing process of the mixed powder and the organic carrier is carried out in a three-roller grinding machine, the rotating speed of the three-roller grinding machine is 380r/min, and the grinding and mixing time is 3 h;
in the high-temperature resistance coating, the mass percent of an organic carrier is 22%, and the organic carrier consists of 78% of tributyl citrate, 6% of cellulose nitrate and 16% of lecithin; the viscosity of the high-temperature resistance coating was 180 pas.
The titanium alloy material flat plate sample coated with the composite coating on the surface prepared in the embodiment is shown in fig. 4, wherein the thickness of the coating is only 1.14mm, and the bonding strength at normal temperature reaches 9.5 MPa. As shown in fig. 5, when the average temperature of the surface of the coating is 665 ℃, the average temperature of the metal substrate is only 500 ℃, the short-time heat insulation reaches 165 ℃, and the coating has excellent heat insulation performance. The normal temperature and high temperature reflectivity curve is shown in figure 6, the normal temperature is lower than-4.20 dB at 8-18 GHz, the normal temperature is lower than-4.85 dB at 8-18 GHz at 550 ℃, and the high temperature wave absorbing performance and the high temperature stability are excellent. The coating is subjected to cold and hot circulation from room temperature to 650 ℃ for more than 200 times, and the cold and hot circulation from room temperature to 550 ℃ for more than 500 times. Therefore, the coating prepared by the embodiment has excellent heat insulation and thermal shock resistance and heat insulation/radar wave absorption integrated functions.
Example 2
A titanium alloy material with a surface coated with a composite coating comprises a titanium alloy substrate and the composite coating coated on the surface of the titanium alloy substrate, wherein the composite coating is a thermal insulation/radar wave absorption integrated composite coating with a four-layer laminated structure, and sequentially comprises a CoCrAlY metal bonding layer, a 15% aluminum oxide-lanthanum zirconate composite thermal insulation ceramic layer, a radar wave absorption layer and a zirconium zirconate composite thermal insulation ceramic layer from inside to outsideThe lanthanum acid diffusion-proof ceramic layer; the thickness of the metal bonding layer is 0.08mm, the thickness of the 15% aluminum oxide-lanthanum zirconate composite heat-insulating ceramic layer is 0.90mm, the thickness of the radar absorbing layer is 0.02mm, the thickness of the lanthanum zirconate ceramic layer is 0.14mm, and the total thickness of the coating is 1.14 mm. Bi used for radar wave absorbing layer with patch type periodic characteristic arrangement2O3-SiO2-B2O3The resistive high-temperature electromagnetic periodic structure layer is a resistive high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a binder phase and bismuth ruthenate-Ag as a conductive phase, wherein the mass of the conductive phase accounts for 60% of the total mass of the conductive phase and the binder phase, and the mass ratio of the bismuth ruthenate to the Ag in the conductive phase is 70: 30; the periodic dimension a of the resistive high-temperature electromagnetic periodic structure layer is 13mm, the side length a.x of the patch is 0.75.
The preparation method of the titanium alloy material with the surface coated with the composite coating comprises the following steps:
(1) coarsening a titanium alloy substrate: roughening the titanium alloy substrate by adopting a sand blasting process, wherein the sand blasting pressure is controlled to be 0.35MPa, the sand blasting distance is controlled to be 100mm, the sand grain size is 60-100 mu m, and the sand blasting time is 2 min;
(2) and (2) spraying a CoNiCrAlY metal bonding layer on the surface of the titanium alloy substrate in the step (1) by adopting an atmospheric plasma spraying process, wherein the process parameters are as follows: the argon flow is 40L/min, and the hydrogen flow is 10L/min; the current is controlled to be 530A, and the power is 33 kW; the flow of the powder feeding argon gas is 2.0L/min, and the powder feeding amount is 25 percent; the spraying distance is 100 mm;
(3) spraying 15% of alumina-lanthanum zirconate composite ceramic material on the metal bonding surface obtained in the step (2) by adopting an atmospheric plasma spraying process to obtain a heat-insulating ceramic layer, wherein the process parameters are as follows: the argon flow is 40L/min, and the hydrogen flow is 14L/min; the current is controlled to be 550A, and the power is 40 kW; the flow of the powder-feeding argon gas is 2.0L/min, the powder-feeding amount is 25%, and the spraying distance is 130 mm;
(4) spraying a high-temperature resistance coating on the heat-insulating ceramic layer in the step (3) by adopting a pattern template-air spraying process, and drying and sintering to obtain a resistance type high-temperature electromagnetic periodic structure layer, namely a radar wave-absorbing layer; controlling the pressure to be 0.3MPa in the normal-pressure air spraying process; in the drying process, the drying temperature is controlled to be 160 ℃, and the drying time is 2 hours; the peak sintering temperature is 450 ℃, the heating rate is 20 ℃/min, the sintering time is 40min, and the sintering atmosphere is air;
(5) preparing a lanthanum zirconate ceramic layer on the surface of the radar absorbing layer in the step (4) by adopting an atmosphere plasma spraying process, wherein the process parameters are as follows: the argon flow is 35L/min, and the hydrogen flow is 10.5L/min; the current is controlled to be 550A, and the power is 35 kW; the flow of the powder feeding argon gas is 1.5L/min, and the powder feeding amount is 12.5 percent; the spraying distance was 125 mm.
In the step (3), the preparation method of the 15% alumina-lanthanum zirconate composite ceramic material comprises the following steps:
①, respectively treating the lanthanum oxide and zirconia raw material powder at the high temperature of 1000 ℃ for 8h, sequentially adding a mixture of lanthanum oxide and zirconia with the molar ratio of 1:2.1 and deionized water with the mass percent of 50% into a ball milling tank, and mixing by a wet ball milling process to obtain ceramic slurry;
②, drying the ceramic slurry to obtain dry powder, wherein the drying temperature is 80 ℃, the drying time is 36h, grinding and refining the dry powder, then screening, and performing high-temperature solid-phase synthesis on the screened powder in a high-temperature box type furnace to obtain lanthanum zirconate ceramic powder, wherein the high-temperature solid-phase synthesis temperature is 1400 ℃, and the reaction time is 24 h;
③ mixing 15% of alumina powder and 85% of lanthanum zirconate ceramic powder in the step ②, sequentially adding 60% of deionized water, 1.8% of gum arabic and 2.8% of triammonium citrate, uniformly mixing by a ball milling process, wherein the ball milling rotation speed is 400r/min, and the stirring time is 60h, and preparing spheroidal particles with certain fluidity and uniform particle size distribution by a spray drying process, namely the 15% alumina-lanthanum zirconate composite ceramic material, wherein the spray drying process parameters are that the outlet temperature is 125 ℃, the inlet temperature is 230 ℃, the slurry feeding speed is 2.5L/min, and the rotating speed of an atomizing disc is 22000 r/min.
In the step (4), the high-temperature resistance coating is prepared by the following method: uniformly mixing glass raw material powder, smelting at 1400 ℃ for 4h to obtain a glass melt, then pouring the glass melt into deionized water for quenching to obtain glass slag, ball-milling the glass slag into glass powder, and mixing the glass powder with bismuth ruthenate-Ag composite powder to obtain mixed powder; grinding and mixing the mixed powder and an organic carrier to obtain a high-temperature resistance coating;
the glass raw material powder comprises the following components in percentage by mass: bi2O346％、La2O38％、Al2O34.5％、SiO223％、Li2O 6％、CaO 4.5％、MgO 3％、B2O35％；
Mixing the glass powder and the bismuth ruthenate-Ag composite powder in a planetary gravity mixer, wherein the revolution speed of the planetary gravity mixer is 1200rpm, the rotation speed is 45 percent of the revolution speed, and the mixing time is 45 min; the grinding and mixing process of the mixed powder and the organic carrier is carried out in a three-roller grinding machine, the rotating speed of the three-roller grinding machine is 380r/min, and the grinding and mixing time is 3 h;
in the high-temperature resistance coating, the mass percent of an organic carrier is 22%, and the organic carrier consists of 78% of tributyl citrate, 6% of cellulose nitrate and 16% of lecithin; the viscosity of the high-temperature resistance coating was 180 pas.
The thickness of the heat insulation/radar wave absorption integrated composite coating prepared by the embodiment is 1.14mm, and the normal-temperature bonding strength reaches 9.0 MPa; when the average temperature of the surface of the coating is 665 ℃, the average temperature of the metal substrate is only 562 ℃, the short-time heat insulation reaches 103 ℃, and the coating has excellent heat insulation performance; the dielectric constant film is lower than-4.0 dB at 8-18 GHz at normal temperature and lower than-4.5 dB at 8-18 GHz at 550 ℃, and has excellent high-temperature wave-absorbing performance and high-temperature stability; the number of times of cold and heat cycles of the coating from room temperature to 650 ℃ is more than 80, and the number of times of cold and heat cycles from room temperature to 550 ℃ is more than 400, so that the coating prepared by the embodiment has excellent heat insulation performance and heat insulation/radar wave absorption integrated functions.
Example 3
A titanium alloy material with a composite coating coated on the surface comprises a titanium alloy substrate and the composite coating coated on the surface of the titanium alloy substrate, wherein the composite coating is a thermal insulation/radar wave absorption integrated composite coating with a four-layer laminated structure, and is prepared fromThe radar wave absorbing layer comprises a CoCrAlY metal bonding layer, a 3% aluminum oxide-lanthanum zirconate composite heat-insulating ceramic layer, a radar wave absorbing layer and a lanthanum zirconate anti-diffusion ceramic layer from inside to outside in sequence; the thickness of the metal bonding layer is 0.08mm, the thickness of the 3% aluminum oxide-lanthanum zirconate composite heat-insulating ceramic layer is 0.80mm, the thickness of the radar absorbing layer is 0.02mm, the thickness of the lanthanum zirconate ceramic layer is 0.05mm, and the total thickness of the coating is 0.95 mm. Bi used for radar wave absorbing layer with patch type periodic characteristic arrangement2O3-SiO2-B2O3The resistive high-temperature electromagnetic periodic structure layer is a resistive high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a binder phase and bismuth ruthenate-Ag as a conductive phase, wherein the mass of the conductive phase accounts for 50% of the total mass of the conductive phase and the binder phase, and the mass ratio of the bismuth ruthenate to the Ag in the conductive phase is 70: 30; the periodic dimension a of the resistance type high-temperature electromagnetic periodic structure layer is 12.2mm, the side length a.x of the patch is 0.85.
The preparation method of the titanium alloy material with the surface coated with the composite coating comprises the following steps:
(1) coarsening a titanium alloy substrate: roughening the titanium alloy substrate by adopting a sand blasting process, wherein the sand blasting pressure is controlled to be 0.35MPa, the sand blasting distance is controlled to be 100mm, the sand grain size is 60-100 mu m, and the sand blasting time is 2 min;
(2) and (2) spraying a CoCrAlY metal bonding layer on the surface of the titanium alloy substrate roughened in the step (1) by adopting an atmospheric plasma spraying process, wherein the process parameters are as follows: the argon flow is 40L/min, and the hydrogen flow is 8L/min; the current is controlled to be 500A, and the power is 32 kW; the flow of the powder feeding argon gas is 2.0L/min, and the powder feeding amount is 25 percent; the spraying distance is 100 mm;
(3) and (3) spraying an alumina-lanthanum zirconate composite ceramic material on the metal bonding surface obtained in the step (2) by adopting an atmospheric plasma spraying process to obtain a heat-insulating ceramic layer, wherein the process parameters are as follows: the argon flow is 40L/min, and the hydrogen flow is 14L/min; the current is controlled to be 550A, and the power is 40 kW; the flow of the powder-feeding argon gas is 2.0L/min, the powder-feeding amount is 25%, and the spraying distance is 130 mm;
(4) spraying a high-temperature resistance coating on the heat-insulating ceramic layer in the step (3) by adopting a pattern template-air spraying process, and drying and sintering to obtain a resistance type high-temperature electromagnetic periodic structure layer, namely a radar wave-absorbing layer; controlling the pressure to be 0.3MPa in the normal-pressure air spraying process; in the drying process, the drying temperature is controlled to be 160 ℃, and the drying time is 2 hours; the peak sintering temperature is 450 ℃, the heating rate is 20 ℃/min, the sintering time is 40min, and the sintering atmosphere is air;
(5) preparing a lanthanum zirconate ceramic layer on the surface of the radar absorbing layer in the step (4) by adopting an atmosphere plasma spraying process, wherein the process parameters are as follows: the argon flow is 35L/min, and the hydrogen flow is 10.5L/min; the current is controlled to be 550A, and the power is 35 kW; the flow of the powder feeding argon gas is 1.5L/min, and the powder feeding amount is 12.5 percent; the spraying distance was 125 mm.
In the step (3), the preparation method of the 3% alumina-lanthanum zirconate composite ceramic material comprises the following steps:
①, respectively treating the lanthanum oxide and zirconia raw material powder at the high temperature of 1000 ℃ for 8h, sequentially adding a mixture of lanthanum oxide and zirconia with the molar ratio of 1:2 and deionized water with the mass percent of 50% into a ball milling tank, and mixing by a wet ball milling process to obtain ceramic slurry;
②, drying the ceramic slurry to obtain dry powder, wherein the drying temperature is 80 ℃, the drying time is 36h, grinding and refining the dry powder, then screening, and carrying out high-temperature solid-phase synthesis on the screened powder in a high-temperature box type furnace to obtain lanthanum zirconate ceramic powder, wherein the high-temperature solid-phase synthesis temperature is 1400 ℃, and the reaction time is 24 h;
③ mixing 3% of alumina powder with 97% of lanthanum zirconate ceramic powder in the step ②, sequentially adding 60% of deionized water, 1.8% of gum arabic and 2.8% of triammonium citrate, uniformly mixing by a ball milling process, wherein the ball milling rotation speed is 400r/min, and the stirring time is 60h, and preparing spheroidal particles with certain fluidity and uniform particle size distribution by a spray drying process, namely the 3% alumina-lanthanum zirconate composite ceramic material, wherein the spray drying process parameters are that the outlet temperature is 125 ℃, the inlet temperature is 230 ℃, the slurry feeding speed is 2.5L/min, and the rotating speed of an atomizing disc is 22000 r/min.
In the step (4), the high-temperature resistance coating is prepared by the following method: uniformly mixing glass raw material powder, smelting at 1400 ℃ for 4h to obtain a glass melt, then pouring the glass melt into deionized water for quenching to obtain glass slag, ball-milling the glass slag into glass powder, and mixing the glass powder with bismuth ruthenate-Ag composite powder to obtain mixed powder; grinding and mixing the mixed powder and an organic carrier to obtain a high-temperature resistance coating;
the glass raw material powder comprises the following components in percentage by mass: bi2O346％、La2O38％、Al2O34.5％、SiO223％、Li2O 6％、CaO 4.5％、MgO 3％、B2O35％；
Mixing the glass powder and the bismuth ruthenate-Ag composite powder in a planetary gravity mixer, wherein the revolution speed of the planetary gravity mixer is 1200rpm, the rotation speed is 45 percent of the revolution speed, and the mixing time is 45 min; the grinding and mixing process of the mixed powder and the organic carrier is carried out in a three-roller grinding machine, the rotating speed of the three-roller grinding machine is 380r/min, and the grinding and mixing time is 3 h;
in the high-temperature resistance coating, the mass percent of an organic carrier is 22%, and the organic carrier consists of 78% of tributyl citrate, 6% of cellulose nitrate and 16% of lecithin; the viscosity of the high-temperature-resistance coating was 180pa · s.
The thickness of the heat insulation/radar wave absorption integrated composite coating prepared by the embodiment is 0.95mm, and the normal-temperature bonding strength reaches 10.5 MPa; when the average temperature of the surface of the coating is 665 ℃, the average temperature of the metal substrate is only 574 ℃, the short-time heat insulation reaches 91 ℃, and the coating has excellent heat insulation performance; the dielectric constant film is lower than-3.5 dB at 8-18 GHz at normal temperature and lower than-3.8 dB at 8-18 GHz at 550 ℃, and has excellent high-temperature wave absorbing performance and high-temperature stability; the number of times of cold and heat circulation from room temperature to 650 ℃ is more than 150, and the number of times of cold and heat circulation from room temperature to 550 ℃ is more than 500, so that the coating prepared by the embodiment has excellent heat insulation performance and heat insulation/radar wave absorption integrated function.
Example 4
A titanium alloy material coated with a composite coating on the surface comprises a titanium alloy substrate and a titanium alloy coating layerThe composite coating is a thermal insulation/radar wave absorption integrated composite coating with a quadruple-layer laminated structure and sequentially comprises a CoNiCrAlY metal bonding layer, a 10% aluminum oxide-gadolinium zirconate composite thermal insulation ceramic layer, a radar wave absorption layer and a gadolinium zirconate anti-diffusion ceramic layer from inside to outside; the thickness of the metal bonding layer is 0.08mm, the thickness of the 10% aluminum oxide-gadolinium zirconate composite heat-insulating ceramic layer is 0.80mm, the thickness of the radar absorbing layer is 0.02mm, the thickness of the lanthanum zirconate ceramic layer is 0.08mm, and the total thickness of the coating is 0.98 mm. Bi used for radar wave absorbing layer with patch type periodic characteristic arrangement2O3-SiO2-B2O3The resistive high-temperature electromagnetic periodic structure layer is a resistive high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a binder phase and bismuth ruthenate-Ag as a conductive phase, wherein the mass of the conductive phase accounts for 60% of the total mass of the conductive phase and the binder phase, and the mass ratio of the bismuth ruthenate to the Ag in the conductive phase is 90: 10; the periodic dimension a of the resistance type high-temperature electromagnetic periodic structure layer is 15mm, the side length a.x of the patch is 0.75.
The preparation method of the titanium alloy material with the surface coated with the composite coating comprises the following steps:
(1) coarsening a titanium alloy substrate: roughening the titanium alloy substrate by adopting a sand blasting process, wherein the sand blasting pressure is controlled to be 0.5MPa, the sand blasting distance is controlled to be 130mm, the sand grain size is 80-120 mu m, and the sand blasting time is 3 min;
(2) and (2) spraying a CoNiCrAlY metal bonding layer on the surface of the titanium alloy substrate in the step (1) by adopting an atmospheric plasma spraying process, wherein the process parameters are as follows: the argon flow is 35L/min, and the hydrogen flow is 8L/min; the current is controlled to be 500A, and the power is 30 kW; the flow of the powder feeding argon gas is 1.5L/min, and the powder feeding amount is 15 percent; the spraying distance is 100 mm;
(3) and (3) spraying 10% of aluminum oxide-gadolinium zirconate composite ceramic material on the metal bonding surface obtained in the step (2) by adopting an atmospheric plasma spraying process to obtain a heat-insulating ceramic layer, wherein the process parameters are as follows: the argon flow is 35L/min, and the hydrogen flow is 12L/min; the current is controlled to be 580A, and the power is 38 kW; the flow of the powder-feeding argon gas is 3.5L/min, the powder-feeding amount is 20 percent, and the spraying distance is 120 mm;
(4) spraying a high-temperature resistance coating on the heat-insulating ceramic layer in the step (3) by adopting a pattern template-air spraying process, and drying and sintering to obtain a resistance type high-temperature electromagnetic periodic structure layer, namely a radar wave-absorbing layer; controlling the pressure to be 0.4MPa in the normal-pressure air spraying process; in the drying process, the drying temperature is controlled to be 200 ℃, and the drying time is 0.5 h; the peak sintering temperature is 550 ℃, the temperature rising speed is 25 ℃/min, the sintering time is 30min, and the sintering atmosphere is air;
(5) preparing a gadolinium zirconate anti-diffusion ceramic layer on the surface of the radar absorbing layer in the step (4) by adopting an atmosphere plasma spraying process, wherein the process parameters are as follows: the argon flow is 35L/min, and the hydrogen flow is 9L/min; the current is controlled to be 550A, and the power is 32 kW; the flow of the powder feeding argon gas is 1.5L/min, and the powder feeding amount is 12.5 percent; the spraying distance was 130 mm.
In the step (3), the preparation method of the 10% aluminum oxide-gadolinium zirconate composite ceramic material comprises the following steps:
① respectively treating the gadolinium oxide and zirconia raw material powder at 1000 ℃ for 8h, sequentially adding a mixture of gadolinium oxide and zirconia with a molar ratio of 1:2.1 and 50% by mass of deionized water into a ball milling tank, and mixing by a wet ball milling process to obtain ceramic slurry;
②, drying the ceramic slurry to obtain dry powder, wherein the drying temperature is 95 ℃, the drying time is 28h, grinding and refining the dry powder, then screening, and carrying out high-temperature solid-phase synthesis on the screened powder in a high-temperature box type furnace to obtain gadolinium zirconate ceramic powder, wherein the high-temperature solid-phase synthesis temperature is 1500 ℃, and the reaction time is 20 h;
③, mixing 10% of alumina powder and 90% of gadolinium zirconate ceramic powder in the step ② by mass percent, sequentially adding 55% of deionized water, 1.2% of arabic gum powder and 2% of triammonium citrate by mass percent, uniformly mixing by a ball milling process, wherein the ball milling rotation speed is 400r/min, and the stirring time is 60 hours, and preparing spheroidal particles with certain fluidity and uniform particle size distribution by a spray drying process, namely the 10% alumina-gadolinium zirconate composite ceramic material, wherein the spray drying process parameters are that the outlet temperature is 120 ℃, the inlet temperature is 220 ℃, the slurry feeding speed is 1.5L/min, and the rotating speed of an atomizing disc is 18000 r/min.
In the step (4), the high-temperature resistance coating is prepared by the following method: uniformly mixing glass raw material powder, smelting at 1500 ℃ for 1h to obtain a glass melt, then pouring the glass melt into deionized water for quenching to obtain glass slag, ball-milling the glass slag into glass powder, and mixing the glass powder with bismuth ruthenate-Ag composite powder to obtain mixed powder; grinding and mixing the mixed powder and an organic carrier to obtain a high-temperature resistance coating;
the glass raw material powder comprises the following components in percentage by mass: bi2O342％、Gd2O39％、Al2O34％、SiO227％、Li2O 5％、CaO 5％、MgO 3％、B2O35％；
Mixing the glass powder and the bismuth ruthenate-Ag composite powder in a planetary gravity mixer, wherein the revolution speed of the planetary gravity mixer is 1200rpm, the rotation speed is 35 percent of the revolution speed, and the mixing time is 50 min; the grinding and mixing process of the mixed powder and the organic carrier is carried out in a three-roller grinding machine, the rotating speed of the three-roller grinding machine is 400r/min, and the grinding and mixing time is 2 hours;
in the high-temperature resistance coating, the mass percent of an organic carrier is 25%, and the organic carrier consists of 85% of tributyl citrate, 4% of cellulose nitrate and 11% of lecithin; the viscosity of the high-temperature-resistance coating was 200pa · s.
The thickness of the heat insulation/radar wave absorption integrated composite coating prepared by the embodiment is 0.98mm, and the normal-temperature bonding strength reaches 10 MPa. When the average temperature of the surface of the coating is 665 ℃, the average temperature of the metal substrate is only 586 ℃, the short-time heat insulation reaches 79 ℃, and the coating has excellent heat insulation performance. The normal temperature is lower than-4.0 dB at 8-18 GHz, the normal temperature is lower than-4.1 dB at 8-18 GHz at 550 ℃, and the high-temperature wave-absorbing performance and the high-temperature stability thereof are excellent. The coating is subjected to cold and hot circulation from room temperature to 650 ℃ for more than 150 times, and is subjected to cold and hot circulation from room temperature to 550 ℃ for more than 500 times. Therefore, the coating prepared by the embodiment has excellent heat insulation performance and heat insulation/radar wave absorption integrated function.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. The utility model provides a thermal-insulated radar wave-absorbing integration composite coating, composite coating is multilayer stack structure, its characterized in that, composite coating includes metal adhesive layer, thermal-insulated ceramic layer, radar absorbing layer and anti-diffusion ceramic layer from inside to outside in proper order, thermal-insulated ceramic layer is compound ceramic layer of aluminium oxide-tombarthite zirconate, radar absorbing layer is for what SMD periodic characteristic arranged with Bi2O3-SiO2-B2O3The high-temperature electromagnetic periodic structure is a resistance type high-temperature electromagnetic periodic structure layer with low-melting-point lead-free glass as a bonding phase and bismuth ruthenate-Ag as a conductive phase, and the anti-diffusion ceramic layer is a rare earth zirconate layer.
2. The heat insulation/radar wave absorption integrated composite coating as claimed in claim 1, wherein the thickness of the metal bonding layer is 0.03 mm-0.08 mm; the thickness of the heat-insulating ceramic layer is 0.70 mm-0.95 mm; the thickness of the radar wave absorbing layer is 0.01 mm-0.03 mm; the thickness of the anti-diffusion ceramic layer is 0.03 mm-0.14 mm.
3. The thermal insulation/radar wave absorption integrated composite coating according to claim 1, wherein the metal bonding layer is a NiCrAlY, CoCrAlY or CoNiCrAlY layer; in the alumina-rare earth zirconate composite ceramic layer, the mass ratio of alumina to rare earth zirconate is 2: 98-20: 80, and the rare earth zirconate is lanthanum zirconate, gadolinium zirconate or samarium zirconate.
4. The thermal insulation/radar wave absorption integrated composite coating as claimed in claim 1, wherein in the resistance type high-temperature electromagnetic periodic structure layer, the mass of the conductive phase accounts for 40-70% of the total mass of the conductive phase and the binder phase, and the mass ratio of bismuth ruthenate to Ag in the conductive phase is (50-90): (10-50).
5. The thermal insulation/radar wave absorption integrated composite coating as claimed in claim 1, wherein the periodic dimension a of the resistance type high-temperature electromagnetic periodic structure layer is 5-45 mm.
6. The titanium alloy material coated with the composite coating on the surface is characterized by comprising a titanium alloy substrate and the composite coating coated on the surface of the titanium alloy substrate, wherein the composite coating is the heat insulation/radar wave absorption integrated composite coating in any one of claims 1 to 5.
7. The method for preparing the titanium alloy material with the surface coated with the composite coating according to claim 6, characterized by comprising the following steps:
(1) roughening the surface of the titanium alloy substrate;
(2) preparing a metal bonding layer on the titanium alloy substrate roughened in the step (1) by adopting an atmospheric plasma spraying process;
(3) coating the alumina-rare earth zirconate composite ceramic material on the metal bonding layer obtained in the step (2) by adopting an atmospheric plasma spraying process to obtain a heat-insulating ceramic layer;
(4) coating the high-temperature resistance coating on the heat-insulating ceramic layer in the step (3) by a pattern template-air spraying process, and drying and sintering to obtain a radar wave-absorbing layer;
(5) and (4) preparing an anti-diffusion ceramic layer on the surface of the radar wave absorbing layer in the step (4) by adopting an atmosphere plasma spraying process to finish the preparation of the titanium alloy material with the surface coated with the composite coating.
8. The production method according to claim 7, wherein in the step (1), the roughening treatment is: placing the titanium alloy substrate in a sand blasting machine for sand blasting and coarsening, wherein the sand blasting and coarsening process parameters are as follows: controlling the pressure to be 0.3-0.6 MPa, controlling the sand blasting distance to be 40-150 mm, controlling the sand grain diameter to be 60-120 mu m, and controlling the sand blasting time to be 1-6 min;
in the step (2), the parameters of the atmospheric plasma spraying process are as follows: the flow rate of argon gas is 35-50L/min, and the flow rate of hydrogen gas is 6-12L/min; the current is controlled to be 450-530A, and the power is 28-35 kW; the flow of the powder-feeding argon is 1.0-3.0L/min, and the powder-feeding amount is 15-35%; the spraying distance is 80-150 mm;
in the step (3), the parameters of the atmospheric plasma spraying process are as follows: the flow rate of argon gas is 35-45L/min, and the flow rate of hydrogen gas is 10-15L/min; the current is controlled to be 530-620A, and the power is 30-45 kW; the flow of the powder-feeding argon is 2.0-5.0L/min, and the powder-feeding amount is 5% -35%; the spraying distance is 80-200 mm;
in the step (4), the pressure of air spraying is 0.1-0.6 MPa; the drying temperature is 130-200 ℃, and the drying time is 0.5-5 h; the sintering process parameters are as follows: the peak sintering temperature is 300-600 ℃, the temperature rising speed is 20-25 ℃/min, the sintering time is 10-60 min, and the sintering atmosphere is air;
in the step (5), the parameters of the atmospheric plasma spraying process are as follows: the flow rate of argon gas is 30-45L/min, and the flow rate of hydrogen gas is 7-12L/min; the current is controlled to be 500-600A, and the power is 25-40 kW; the flow of the powder-feeding argon is 1.0-4.0L/min, and the powder-feeding amount is 5% -30%; the spraying distance is 80-200 mm.
9. The method according to claim 7, wherein in the step (3), the alumina-rare earth zirconate composite ceramic material is prepared by a method comprising the following steps:
①, performing high-temperature heat treatment on the rare earth oxide and zirconia raw material powder, sequentially adding the rare earth oxide, zirconia and deionized water into a ball milling tank according to a stoichiometric ratio, and mixing by a wet ball milling process to obtain ceramic slurry;
②, drying the ceramic slurry to obtain dry powder, grinding and refining the dry powder, then screening, and carrying out high-temperature solid-phase synthesis on the screened powder to obtain rare earth zirconate ceramic powder;
Figure 68075DEST_PATH_IMAGE001
mixing alumina powder with the rare earth zirconate ceramic powder obtained in the step ②, sequentially adding deionized water, arabic gum powder and triammonium citrate, uniformly mixing through a ball milling process, and preparing the alumina-rare earth zirconate composite ceramic material through a spray drying process;
in the step ①, the high-temperature heat treatment temperature is 800-1200 ℃, the heat treatment time is 2-12 hours, the molar ratio of the rare earth oxide to the zirconia is 1 (2-2.2), and the mass percent of the deionized water is 45-60%;
in the step ②, the drying temperature is 60-100 ℃, the drying time is 24-48 h, the high-temperature solid phase synthesis temperature is 1200-1600 ℃, and the reaction time is 12-72 h;
said step (c) is
Figure 463284DEST_PATH_IMAGE001
In the preparation method, the mass ratio of the alumina powder to the rare earth zirconate ceramic powder is 2: 98-20: 80, the mass percent of deionized water is 40-70%, the mass percent of the Arabic gum powder is 0.5-5%, and the mass percent of the triammonium citrate is 0.5-5%; the ball milling rotation speed is 250-450 r/min, and the stirring time is 48-72 h; the spray drying process parameters are as follows: the outlet temperature is 100-170 ℃, the inlet temperature is 150-280 ℃, the slurry feeding speed is 0.5-5.0L/min, and the rotation speed of the atomizing disc is 12000-25000 r/min.
10. The method according to claim 7, wherein in the step (4), the high-temperature resistance coating is prepared by: uniformly mixing glass raw material powder, smelting at 1200-1500 ℃ for 1-6 h to obtain a glass melt, then pouring the glass melt into deionized water for quenching to obtain glass slag, ball-milling the glass slag into glass powder, uniformly mixing the glass powder with bismuth ruthenate-Ag composite powder to obtain mixed powder, and mixing and grinding the mixed powder with an organic carrier to prepare a high-temperature resistance coating;
the glass raw material powder mainly comprises the following components in percentage by mass: bi2O340%~50%、Re2O35%～9%、Al2O34%～5%、SiO210%～30%、Li2O 4%～8%、CaO 3%～5%、MgO 1%～5%、B2O33% -6%, and Re is a rare earth element;
the mixing process of the glass powder and the bismuth ruthenate-Ag composite powder is carried out in a planetary gravity mixer, the revolution speed of the planetary gravity mixer is 1000-1400 rpm, the rotation speed is 20-50% of the revolution speed, and the mixing time is 40-80 min;
mixing and grinding the mixed powder and the organic carrier in a three-roller grinding machine, wherein the rotating speed of the three-roller grinding machine is 200-400 r/min, and the grinding and mixing time is 1-6 h;
the high-temperature resistance coating comprises 20-30% of an organic carrier by mass, wherein the organic carrier mainly comprises 75-85% of tributyl citrate by mass, 4-7% of cellulose nitrate by mass and 11-18% of lecithin by mass; the viscosity of the high-temperature resistance coating is 100-250 Pa · s.
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