CN110396002B - Preparation method of high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating - Google Patents

Preparation method of high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating Download PDF

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CN110396002B
CN110396002B CN201910753839.5A CN201910753839A CN110396002B CN 110396002 B CN110396002 B CN 110396002B CN 201910753839 A CN201910753839 A CN 201910753839A CN 110396002 B CN110396002 B CN 110396002B
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朱时珍
李奕臻
柳彦博
马壮
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Beijing Institute of Technology BIT
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5062—Borides, Nitrides or Silicides
    • C04B41/507—Borides
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • C04B41/85—Coating or impregnation with inorganic materials

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Abstract

The invention relates to a preparation method of a high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating, belonging to the technical field of composite materials and coating preparation. In the method, submicron powder is used as a raw material, and spray granulation and plasma spheroidization technologies are combined to obtain ZrB with good sphericity, high density, good fluidity and high apparent density2‑SiC‑La2O3The powder for plasma spraying is prepared into a coating with high density by a plasma spraying technology, the coating can bear ablation examination for 300s at the surface temperature of 2000 ℃, and the application requirement under the high-temperature aerobic ablation environment can be met.

Description

Preparation method of high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating
Technical Field
The invention particularly relates to a preparation method of a high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating, belonging to the technical field of composite materials and coating preparation.
Background
The carbon fiber reinforced carbon matrix composite (C/C) has high specific strength, high specific modulus, corrosion resistance, high temperature resistance, low density and good high-temperature mechanical property and thermal property, and is an ideal thermal structure material in the field of aerospace. However, in the face of the working environment of high temperature, high pressure, high speed and oxygen-containing airflow in the service process of the aircraft, the carbonaceous material in the carbon matrix composite material is easily oxidized (the aerobic environment above 400 ℃ begins to be oxidized), and the performance of the material is difficult to maintain for a long time. Aiming at the problem of high-temperature oxidation ablation of the carbon matrix composite material, an anti-oxidation ablation-resistant coating is often prepared on the surface of the carbon matrix composite material so as to achieve an effective protection effect.
ZrB2the-SiC coating is an antioxidant ablation-resistant coating material system which is widely researched in recent years, and the protection temperature range of the material is widened by compounding two materials. Boride potteryB of porcelain formation2O3The melting point is low (450 ℃), and the volatilization is serious above 1200 ℃, which causes the structural damage of the coating. The oxidation rate of SiC is slow in the temperature range of 800-1200 ℃, and the generated SiO2The amount is small and the viscosity is high, so that a good sealing effect cannot be achieved. ZrB2the-SiC coating is slowly oxidized at the temperature of 800-1200 ℃ to generate ZrO2And B2O3At this time, B2O3The viscosity is suitable and can be used as a sealing and filling phase. SiO generated by oxidation of SiC at the temperature of 1200-1600 DEG C2Playing a role of sealing and filling. Furthermore, ZrO2With SiO2Formation of ZrSiO at high temperatures4The particles can also play a role in nail rolling and slowing down SiO2The volatilization prolongs the protection time of the coating. The researchers studied ZrB2-effect of relative proportions of the two materials in the SiC coating on coating properties, results show ZrB with 20-30 vol.% SiC2The SiC coating has the best oxidation resistance. Further, the higher the uniformity of SiC distribution per unit area, the more SiO is generated by oxidation2At ZrO2The more uniform the distribution is, so that SiO2More effectively fills the holes and closes the defects so as to block the oxygen from entering and improve the oxidation resistance of the material. But ZrB in an aerobic ablation environment at a temperature higher than 1800 DEG C2Reactive oxidation of silicon carbide in SiC coatings and SiO at high temperatures2Leads to the coating finally only to retain unsintered compact loose zirconia (ZrO) during high-temperature service2) The skeleton, thereby losing the protective effect. Therefore, it is necessary to modify the zirconium diboride-silicon carbide system appropriately to overcome the above disadvantages, thereby meeting the service requirements in a higher temperature aerobic ablation environment.
The plasma flame flow generated by the plasma spraying technology has high temperature and concentrated heat, and is very suitable for preparing the oxidation-resistant and ablation-resistant coating. However, zirconium diboride and silicon carbide have high melting points, are covalent compounds, have low self-diffusion coefficients and are difficult to sinter, so that a compact coating is difficult to obtain. In addition, the existing powder for plasma spraying is mainly prepared by adopting micron-sized raw material powder through ball milling powder mixing and spray granulation processes to prepare agglomerated powder, and then the agglomerated powder is sintered by adopting a sintering process to improve the mechanical strength and compactness of the powder. Because the two powders of zirconium diboride and silicon carbide have high melting points and are difficult to sinter, the compactness and the mechanical strength of the powder cannot be effectively improved by sintering treatment. The powder obtained by the process has a loose structure, a rough surface and low strength, and is easy to break and difficult to melt during the conveying in the coating preparation process. Meanwhile, because the raw material powder particles are large, the problems of more gaps, loose structure and the like exist in the anti-oxidation ablation coating prepared by the atmospheric plasma spraying system, and the particles are low in distribution uniformity on a microscale and are not beneficial to maintaining the anti-ablation performance of the coating.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating, and on one hand, ZrB is improved by adding lanthanum oxide2The ablation resistance and compactness of the SiC coating, and on the other hand, the particle size, sphericity and compactness of the sprayed powder are optimized to meet the requirements of plasma spraying, so that the coating which has high compactness and meets the requirements under a high-temperature aerobic ablation environment is obtained.
The purpose of the invention is realized by the following technical scheme.
A method for preparing a high temperature oxidation and ablation resistant dense coating based on a non-oxide, said method comprising the steps of:
step 1, uniformly mixing zirconium diboride powder, silicon carbide powder and lanthanum oxide powder with the particle size of 200-500 nm with polyvinyl alcohol (PVA) and water to obtain suspension;
in the suspension, the mass percent of polyvinyl alcohol is 0.1-0.3%, the sum of the mass percent of the three powders is 39-60%, the volume ratio of zirconium diboride powder to silicon carbide powder is 7:3, and the volume percent of lanthanum oxide powder in the three powders is 5-20%;
furthermore, the sum of the mass percentages of the three powders in the suspension is preferably 39-42%; the volume percentage of the lanthanum oxide powder in the three kinds of powder is preferably 10-15%;
further, mixing raw material powder by adopting a ball milling mode, carrying out ball milling for 4-6 h at 200-500 r/min, wherein the ball-material ratio is 4-5: 1, and uniformly mixing all the components to obtain a suspension;
step 2, conveying the suspension into a spray drying granulation tower for spray granulation, drying the granulated powder and screening the dried powder to obtain ZrB with the grain diameter of 20-90 mu m2-SiC-La2O3Agglomerating the powder;
spray drying granulation process parameters: the inlet temperature is 280-330 ℃, the outlet temperature is 110-140 ℃, the rotating speed of the spray head is 25-40 Hz, and the rotating speed of the peristaltic pump is 35-45 rpm;
further, drying the granulated powder at 100-150 ℃;
step 3, ZrB2-SiC-La2O3Sending the agglomerated powder into plasma spheroidizing equipment for spheroidizing, and sieving the spheroidized powder by using a test sieve to obtain ZrB with the particle size of 10-70 mu m2-SiC-La2O3Spheroidizing the powder;
plasma spheroidization process parameters: the flow rate of main gas (argon) is 65 SCFH-70 SCFH, and auxiliary gas (H)2) The flow rate is 5SCFH to 8SCFH, the flow rate of carrier gas (argon) is 2SCFH to 5SCFH, the powder feeding rate is 4.5RPM to 5.5RPM, the pressure of a treatment chamber is 14psia to 16psia, and the power is 35kW to 40 kW;
step 4, ZrB is sprayed by adopting an atmosphere plasma spraying process2-SiC-La2O3The spheroidized powder is sprayed on a substrate to form ZrB on the substrate2-SiC-La2O3Coating;
the technological parameters of the atmospheric plasma spraying are as follows: the spraying distance is 80-110 mm, the current is 700-900A, the flow rate of main gas (argon) is 70-90 SCFH, the flow rate of auxiliary gas (helium) is 30-50 SCFH, the flow rate of carrier gas (argon) is 8-12 SCFH, and the powder feeding rate is 2-4 RPM.
Further, the thickness of the coating is 0.1 mm-0.3 mm.
Has the advantages that:
(1) the invention selects powder with particle size of submicron (200 nm-500 nm) as raw material powder, the reduction of the particle size is beneficial to more sufficient fusion among the powder in the spheroidization process, so that the distribution of each component is more uniform, and the oxidation resistance and the ablation resistance of the coating are improved;
(2) according to the invention, lanthanum oxide is selected as an additive, the melting point of the lanthanum oxide is about 2300 ℃, the melting point of the lanthanum oxide is lower than that of zirconium diboride and silicon carbide powder, the melting point of the lanthanum oxide is close to the eutectic temperature of the zirconium diboride and the silicon carbide, and the lanthanum oxide can be used as a low-melting-point phase to fill pores and cracks in the powder, so that the compactness of the coating is improved; the melting point of lanthanum oxide is between that of silicon dioxide generated by silicon carbide oxidation and zirconium oxide generated by zirconium boride oxidation, loss caused by volatilization of silicon element in the ablation process can be compensated, meanwhile, lanthanum oxide can promote densification of zirconium oxide at high temperature, so that the generated ablation layer can be kept dense at higher temperature for longer time, and the oxidation resistance and ablation resistance of the coating are improved;
(3) in the invention, plasma spheroidization technology is adopted to carry out densification treatment on the powder after spray granulation, so that the spheroidized powder has good sphericity, high density, good fluidity and high apparent density, the density and cohesion of the powder are improved, and the requirement of plasma spraying is met;
(4) the coating prepared by the method has high density, the oxidation resistance and ablation resistance of the coating are improved, the coating can bear ablation examination at the surface temperature of 2000 ℃ for 300s, and the technical bottleneck of 1800 ℃ is broken through.
Drawings
FIG. 1 is ZrB prepared in example 42-SiC-La2O3A surface Scanning Electron Microscope (SEM) image and a surface scanning elemental analysis (SEM) image of the spheroidized powder.
FIG. 2 is ZrB prepared in example 42-SiC-La2O3Scanning electron microscope picture of micro particle size distribution of spheroidized powder.
FIG. 3 is ZrB prepared in example 42-SiC-La2O3Section scanning electrode for spheroidizing powderA sub-microscopic image and a surface scanning elemental analysis image.
FIG. 4 is ZrB prepared in example 42-SiC-La2O3Scanning electron microscopy of the surface and cross-section of the coating.
FIG. 5 is ZrB prepared in example 42-SiC-La2O3And (3) carrying out ablation examination on the coating by using oxyacetylene flame flow (the surface temperature is 2000 ℃, and the examination time is 300s) to obtain a surface macro-topography map and a micro-topography map of an ablation central area.
FIG. 6 is ZrB prepared in example 42-SiC-La2O3The X-ray diffraction (XRD) pattern and ZrB of the coating before and after the coating is examined by oxyacetylene flame flow ablation (the surface temperature is 2000 ℃, the examination time is 300s)2、m-ZrO2、c-ZrO2And La2Zr2O7A comparative XRD pattern of (a).
FIG. 7 is a surface macro-topography and a micro-topography of the ablated center area of the coating prepared in comparative example 1 examined by oxyacetylene flame flow ablation (surface temperature 2000 ℃ C., examination time 300 s).
Detailed Description
The invention is further illustrated by the following figures and detailed description, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public disclosure without further specification.
In the following examples:
and (4) SEM characterization: ZrB prepared in the examples was observed by a cold field emission scanning electron microscope of type S-4800, high and New technology, Japan2-SiC-La2O3Spheroidized powder morphology and prepared coating morphology;
x-ray diffraction analysis: ZrB prepared in the examples was subjected to X' Pert PRO MPD type polycrystal X-ray diffraction analyzer manufactured by PANALYtical Co.Netherlands2-SiC-La2O3Analyzing the coating; and (3) testing conditions are as follows: k of CuαRay, Ni filter, tube voltage 40kV, tube current 40mA, slit size DS 0.957 degree, PSD 2.12 degree, scanning speed 4 degree/min;
spray drying prilling tower: an LGZ-8 centrifugal spray dryer of a Wuxi Dongjiang spray granulation drying machinery plant;
induction plasma spheroidization equipment: a40 kW-grade induction Plasma powder spheroidizing system manufactured by TEKNA Plasma Systems Inc., Canada has a model number of PL-35.
Atmosphere plasma spraying equipment: the Praxair GTS-5500 model atmospheric plasma spraying equipment made in America adopts SG-100 as a spray gun and 1264 model powder feeder as a powder feeder.
PVA (polyvinyl alcohol): the purity is more than or equal to 98 percent and is produced by Fosmann technologies (Beijing) Co.
ZrB2: the particle size is 500nm, the purity is more than or equal to 98 percent, and the product is produced by Fusmann technology (Beijing) Co.
SiC: the particle size is 500nm, the purity is more than or equal to 98 percent, and the product is produced by Fusmann technology (Beijing) Co.
La2O3: the particle size is 500nm, the purity is more than or equal to 99.9 percent, and the product is produced by Beijing Huaweiruike chemical industry Co.
The prepared coating is subjected to ablation examination by adopting an oxygen-acetylene flame spraying system, the model of an oxygen-acetylene spray gun is FP-73, the diameter of a nozzle is 2mm, the oxygen pressure is 0.7MPa, the oxygen flow is 25L/min, the acetylene pressure is 0.05MPa, the acetylene flow is 50L/min, the compressed air pressure is 0.3MPa, the examination distance is 25mm, the examination temperature is 2000 ℃, and the examination time is 300 s.
Example 1
(1) Adding 191.5g of zirconium diboride, 43g of silicon carbide, 15.5g of lanthanum oxide, 0.75g of PVA and 375g of deionized water into a ball milling tank, wherein the ball-material ratio is 4:1, and carrying out ball milling at 200r/min for 4 hours to uniformly mix the components to obtain suspension;
(2) transferring the suspension into a spray drying granulation tower for spray granulation, putting the granulated powder into a 100 ℃ oven for drying for 15h, and then performing inspection screening to obtain ZrB with the particle size of 20-90 mu m2-SiC-La2O3Agglomerating the powder;
wherein, the technological parameters of spray drying granulation are as follows: the inlet temperature is 280 ℃, the outlet temperature is 110 ℃, the rotating speed of the spray head is 25Hz, and the rotating speed of the peristaltic pump is 35 rpm;
(3) reacting ZrB2-SiC-La2O3Sending the agglomerated powder into an induction plasma spheroidizing device for spheroidizing, and passing the spheroidized powder through a test sieve to obtain ZrB with the particle size of 10-70 mu m2-SiC-La2O3Spheroidizing the powder;
wherein, the induction plasma spheroidization process parameters are as follows: main gas (argon) flow 70SCFH, auxiliary gas (H)2Gas) flow rate of 8SCFH, carrier gas (argon) flow rate of 5SCFH, powder feeding rate of 4.5RPM, treatment chamber pressure of 16psia and plasma spheroidization power of 40 kW;
(4) ZrB is sprayed by adopting an atmospheric plasma spraying process2-SiC-La2O3The spheroidized powder is sprayed on a C/C composite material substrate to form ZrB with the thickness of about 0.15mm on the substrate2-SiC-La2O3Coating;
wherein, the technological parameters of the atmospheric plasma spraying are as follows: the spraying distance is 80mm, the current is 900A, the flow rate of main gas (argon) is 90SCFH, the flow rate of auxiliary gas (helium) is 50SCFH, the flow rate of carrier gas (argon) is 12SCFH, and the powder feeding rate is 2 RPM.
According to the SEM characterization result, the prepared ZrB2-SiC-La2O3The spheroidized powder is spherical with compact and smooth surface, the particle size distribution is 10-60 mu m, the section is compact, and the porosity is low. Prepared ZrB2-SiC-La2O3The fluidity of the spheroidized powder is 21.62s/50g, and the apparent density is 3.17g/cm3。
Prepared ZrB2-SiC-La2O3The coating has no cracks and is relatively dense, the coating can endure the ablation examination of the surface temperature of 2000 ℃ for 300s, and the mass ablation rate of the coating is 2.31 multiplied by 10-3g/s。
Example 2
(1) Adding 179.25g of zirconium diboride, 40.25g of silicon carbide, 30.5g of lanthanum oxide, 1g of PVA and 375g of deionized water into a ball milling tank, wherein the ball-material ratio is 4:1, and carrying out ball milling for 5 hours at 300r/min to uniformly mix the components to obtain suspension;
(2) transferring the suspension into a spray drying granulation tower for spray granulation, and granulating the granulated powderThe ZrB is dried for 15h in a 120 ℃ oven and then sieved to obtain ZrB with the grain diameter of 20-90 mu m2-SiC-La2O3Agglomerating the powder;
wherein, the technological parameters of spray drying granulation are as follows: the inlet temperature is 290 ℃, the outlet temperature is 120 ℃, the rotating speed of the spray head is 30Hz, and the rotating speed of the peristaltic pump is 35 rpm;
(3) reacting ZrB2-SiC-La2O3Sending the agglomerated powder into an induction plasma spheroidizing device for spheroidizing, and passing the spheroidized powder through a test sieve to obtain ZrB with the particle size of 10-70 mu m2-SiC-La2O3Spheroidizing the powder;
wherein, the induction plasma spheroidization process parameters are as follows: main gas (argon) flow 68SCFH, auxiliary gas (H)2Gas) flow rate of 7SCFH, carrier gas (argon) flow rate of 4SCFH, powder feeding rate of 4.8RPM, treatment chamber pressure of 15.5psia and plasma spheroidization power of 38 kW;
(4) ZrB is sprayed by adopting an atmospheric plasma spraying process2-SiC-La2O3The spheroidized powder is sprayed on a C/C composite material substrate to form ZrB with the thickness of about 0.15mm on the substrate2-SiC-La2O3Coating;
wherein, the technological parameters of the atmospheric plasma spraying are as follows: the spraying distance is 90mm, the current is 850A, the flow rate of main gas (argon) is 80SCFH, the flow rate of auxiliary gas (helium) is 40SCFH, the flow rate of carrier gas (argon) is 10SCFH, and the powder feeding rate is 3 RPM.
According to the SEM characterization result, the prepared ZrB2-SiC-La2O3The spheroidized powder is spherical with compact and smooth surface, the particle size distribution is 10-60 mu m, the section is compact, and the porosity is low. Prepared ZrB2-SiC-La2O3The fluidity of the spheroidized powder is 23.95s/50g, and the apparent density is 2.96g/cm3。
Prepared ZrB2-SiC-La2O3The coating has no cracks and is relatively dense, the coating can endure the ablation examination of the surface temperature of 2000 ℃ for 300s, and the mass ablation rate of the coating is 0.75 multiplied by 10-3g/s。
Example 3
(1) Adding 167.5g of zirconium diboride, 37.5g of silicon carbide, 45g of lanthanum oxide, 1.25g of PVA and 375g of deionized water into a ball milling tank, wherein the ball-material ratio is 5:1, and carrying out ball milling for 5 hours at 400r/min to uniformly mix all the components to obtain suspension;
(2) transferring the suspension into a spray drying granulation tower for spray granulation, putting the granulated powder into a 140 ℃ oven for drying for 18h, and then performing inspection screening to obtain ZrB with the particle size of 20-90 mu m2-SiC-La2O3Agglomerating the powder;
wherein, the technological parameters of spray drying granulation are as follows: the inlet temperature is 320 ℃, the outlet temperature is 130 ℃, the rotating speed of the spray head is 35Hz, and the rotating speed of the peristaltic pump is 40 rpm;
(3) reacting ZrB2-SiC-La2O3Sending the agglomerated powder into an induction plasma spheroidizing device for spheroidizing, and passing the spheroidized powder through a test sieve to obtain ZrB with the particle size of 10-70 mu m2-SiC-La2O3Spheroidizing the powder;
wherein, the induction plasma spheroidization process parameters are as follows: main gas (argon) flow 66SCFH, auxiliary gas (H)2Gas) flow rate of 6SCFH, carrier gas (argon) flow rate of 3SCFH, powder feeding rate of 5.0RPM, treatment chamber pressure of 15psia and plasma spheroidization power of 36 kW;
(4) ZrB is sprayed by adopting an atmospheric plasma spraying process2-SiC-La2O3The spheroidized powder is sprayed on a C/C composite material substrate to form ZrB with the thickness of about 0.15mm on the substrate2-SiC-La2O3Coating;
wherein, the technological parameters of the atmospheric plasma spraying are as follows: the spraying distance was 100mm, the current was 750A, the flow of main gas (argon) was 75SCFH, the flow of auxiliary gas (helium) was 35SCFH, the flow of carrier gas (argon) was 10SCFH, and the powder feed rate was 3.5 RPM.
According to the SEM characterization result, the prepared ZrB2-SiC-La2O3The spheroidized powder is spherical with compact and smooth surface, the particle size distribution is 10-60 mu m, the section is compact, and the porosity is low. Prepared ZrB2-SiC-La2O3The fluidity of the spheroidized powder is 22s/50g, and the apparent density is 3.28g/cm3。
Prepared ZrB2-SiC-La2O3The coating is not cracked and is dense, the coating can endure the ablation examination of the surface temperature of 2000 ℃ for 300s, and the mass ablation rate of the coating is 0.95 multiplied by 10-3g/s。
Example 4
(1) Adding 155.75g of zirconium diboride, 35g of silicon carbide, 59.25g of lanthanum oxide, 1.5g of PVA and 375g of deionized water into a ball milling tank, wherein the ball-material ratio is 5:1, and carrying out ball milling for 6 hours at 500r/min to uniformly mix the components to obtain suspension;
(2) transferring the suspension into a spray drying granulation tower for spray granulation, putting the granulated powder into a drying oven at 150 ℃ for drying for 10 hours, and then performing inspection screening to obtain ZrB with the particle size of 20-90 mu m2-SiC-La2O3Agglomerating the powder;
wherein, the technological parameters of spray drying granulation are as follows: the inlet temperature is 330 ℃, the outlet temperature is 140 ℃, the rotating speed of the spray head is 40Hz, and the rotating speed of the peristaltic pump is 45 rpm;
(3) reacting ZrB2-SiC-La2O3Sending the agglomerated powder into an induction plasma spheroidizing device for spheroidizing, and passing the spheroidized powder through a test sieve to obtain ZrB with the particle size of 10-70 mu m2-SiC-La2O3Spheroidizing the powder;
wherein, the induction plasma spheroidization process parameters are as follows: main gas (argon) flow 65SCFH, auxiliary gas (H)2Gas) flow rate of 5SCFH, carrier gas (argon) flow rate of 2SCFH, powder feeding rate of 5.5RPM, treatment chamber pressure of 14psia and plasma spheroidization power of 35 kW;
(4) ZrB is sprayed by adopting an atmospheric plasma spraying process2-SiC-La2O3The spheroidized powder is sprayed on a C/C composite material substrate, and a coating with the thickness of about 0.15mm is formed on the substrate;
wherein, the technological parameters of the atmospheric plasma spraying are as follows: the spraying distance is 110mm, the current is 700A, the flow of main gas (argon) is 70SCFH, the flow of auxiliary gas (helium) is 30SCFH, the flow of carrier gas (argon) is 8SCFH, and the powder feeding rate is 4 RPM.
As can be seen from FIG. 1, ZrB was produced2-SiC-La2O3The spheroidized powder is in a spherical shape with a compact and smooth surface, and all elements are uniformly distributed. As can be seen from FIG. 2, ZrB was prepared2-SiC-La2O3The grain size distribution of the spheroidized powder is about 10 to 60 mu m. Prepared ZrB2-SiC-La2O3The fluidity of the spheroidized powder is 24.7s/50g, and the apparent density is 3.18g/cm3. As can be seen from FIG. 3, ZrB was produced2-SiC-La2O3The spheroidized powder has compact cross section, low porosity and uniform distribution of elements.
As can be seen from FIG. 4, ZrB was produced2-SiC-La2O3The coating is almost crack-free, has a small amount of gaps and is compact. As can be seen from FIGS. 5 and 6, ZrB was observed after ablation at 2000 ℃ for 300s2-SiC-La2O3Complete coating and new phase La after ablation2Zr2O7The ablation center is in a leveled, dense state. Prepared ZrB2-SiC-La2O3The mass ablation rate of the coating was 2.31X 10-3g/s。
Comparative example 1
(1) Adding 204g of zirconium diboride, 46g of silicon carbide, 0.75g of PVA and 375g of deionized water into a ball milling tank, wherein the ball-to-material ratio is 4:1, and carrying out ball milling for 4 hours at 200r/min to uniformly mix the components to obtain suspension;
(2) transferring the suspension into a spray drying granulation tower for spray granulation, putting the granulated powder into a 100 ℃ oven for drying for 15h, and then performing inspection screening to obtain ZrB with the particle size of 20-90 mu m2-SiC agglomerated powder;
wherein, the technological parameters of spray drying granulation are as follows: the inlet temperature is 280 ℃, the outlet temperature is 110 ℃, the rotating speed of the spray head is 25Hz, and the rotating speed of the peristaltic pump is 35 rpm;
(3) reacting ZrB2Sending the-SiC agglomerated powder into induction plasma spheroidizing equipment for spheroidizing, and passing the spheroidized powder through a test sieve to obtain ZrB with the grain diameter of 10-70 mu m2-SiC spheroidized powder;
wherein, the induction plasma spheroidization process parameters are as follows: main gas (argon) flow 70SCFH, auxiliary gas (H)2Gas) flow rate 8SCFH, carrier gasThe flow rate of (argon gas) is 5SCFH, the powder feeding rate is 4.5RPM, the pressure of the treatment chamber is 16psia, and the power of plasma spheroidization is 40 kW;
(4) ZrB is sprayed by adopting an atmospheric plasma spraying process2Spraying SiC spheroidized powder on a C/C composite material substrate to form ZrB with the thickness of about 0.15mm on the substrate2-a SiC coating;
wherein, the technological parameters of the atmospheric plasma spraying are as follows: the spraying distance is 80mm, the current is 900A, the flow rate of main gas (argon) is 90SCFH, the flow rate of auxiliary gas (helium) is 50SCFH, the flow rate of carrier gas (argon) is 12SCFH, and the powder feeding rate is 2 RPM.
For the prepared ZrB2the-SiC coating was examined by oxy-acetylene flame flow ablation, and fig. 7 shows the macro-morphology of the coating after examination and the micro-morphology of the central region. It was found that La was not added2O3ZrB of2After the-SiC coating is ablated and examined at 2000 ℃ for 300s, part of the coating falls off, the C/C matrix is exposed, the coating fails, and the microscopic morphology of the coating is represented by the non-compact morphology with holes.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a high-temperature oxidation-resistant ablation-resistant non-oxide-based compact coating is characterized by comprising the following steps: the method consists of the following steps:
step 1, uniformly mixing zirconium diboride powder, silicon carbide powder and lanthanum oxide powder with the particle size of 200-500 nm with polyvinyl alcohol and water to obtain suspension; wherein the volume ratio of the zirconium diboride powder to the silicon carbide powder is 7:3, and the volume percentage of the lanthanum oxide powder in the three powders is 5-20%;
and 2, conveying the suspension into a spray drying granulation tower for spray granulation, drying the granulated powder and screening by a test sieve to obtain ZrB with the particle size of 20-90 mu m2-SiC-La2O3Agglomerating the powder;
step 3, ZrB2-SiC-La2O3Sending the agglomerated powder into plasma spheroidizing equipment for spheroidizing, and screening the spheroidized powder through a test sieve to obtain ZrB with the particle size of 10-70 mu m2-SiC-La2O3Spheroidizing the powder;
step 4, ZrB is sprayed by adopting an atmosphere plasma spraying process2-SiC-La2O3The spheroidized powder is sprayed on a substrate to form ZrB on the substrate2-SiC-La2O3Coating;
in step 4, the parameters of the atmospheric plasma spraying process are as follows: the spraying distance is 80mm ~110mm, and electric current 700A ~ 900A, and main gas argon gas flow is 70SCFH ~90 SCFH, and supplementary gas helium gas flow is 30SCFH ~50 SCFH, and carrier gas argon gas flow is 8SCFH ~12 SCFH, and the powder rate of sending is 2RPM ~4 RPM.
2. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: in the suspension, the mass percent of the polyvinyl alcohol is 0.1-0.3%, and the sum of the mass percent of the zirconium diboride powder, the silicon carbide powder and the lanthanum oxide powder is 39-60%.
3. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 2, characterized in that: the sum of the mass percentages of the zirconium diboride powder, the silicon carbide powder and the lanthanum oxide powder in the suspension is 39-42%.
4. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: the volume of the lanthanum oxide powder accounts for 10-15% of the sum of the volumes of the zirconium diboride powder, the silicon carbide powder and the lanthanum oxide powder.
5. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: in the step 1, ball milling is carried out for 4-6 h at 200-500 r/min, the ball-material ratio is 4-5: 1, and the suspension is obtained after uniform mixing.
6. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: in step 2, spray drying granulation process parameters are as follows: the inlet temperature is 280-330 ℃, the outlet temperature is 110-140 ℃, the rotating speed of the spray head is 25-40 Hz, and the rotating speed of the peristaltic pump is 35-45 rpm.
7. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: in the step 2, drying the granulated powder at the temperature of 100-150 ℃.
8. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: in step 3, plasma spheroidizing process parameters are as follows: the main gas argon gas flow is 65SCFH ~70 SCFH, and the auxiliary gas hydrogen flow is 5SCFH ~ 8SCFH, and the carrier gas argon gas flow is 2SCFH ~ 5SCFH, and the powder rate of sending 4.5RPM ~5.5 RPM, and the treatment chamber pressure 14psia ~16 psia, power are 35kW ~40 kW.
9. The method for preparing a high-temperature oxidation-resistant ablation-resistant non-oxide-based dense coating according to claim 1, characterized in that: ZrB2-SiC-La2O3The thickness of the coating is 0.1 mm-0.3 mm.
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