CN113088109A - High-energy laser ablation resistant composite protective coating and preparation method thereof - Google Patents

High-energy laser ablation resistant composite protective coating and preparation method thereof Download PDF

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CN113088109A
CN113088109A CN202110535567.9A CN202110535567A CN113088109A CN 113088109 A CN113088109 A CN 113088109A CN 202110535567 A CN202110535567 A CN 202110535567A CN 113088109 A CN113088109 A CN 113088109A
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laser ablation
protective coating
coating
energy laser
composite protective
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CN113088109B (en
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汪涛
杨蒙蒙
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The invention discloses a high-energy laser ablation resistant composite protective coating and a preparation method thereof, wherein the composite protective coating is prepared from 10-25% of silicon carbide whiskers, 20-40% of zirconium diboride powder and 45-55% of zirconia sol by mass. The method is characterized in that a proper amount of silicon carbide whisker and zirconium diboride powder are added into zirconia sol and evenly stirred to prepare a coating with a certain viscosity, and the composite coating is coated on an aluminum alloy matrix subjected to surface pretreatment and then dried and cured to obtain the protective coating resistant to high-energy laser ablation. The composite protective coating resistant to high-energy laser ablation has a structure with three-dimensional micropores with the pore size of 5-20 mu m, and can effectively resist 7kW/cm2Laser irradiation, after 10s laser irradiation, the substrate at the center of laser ablation is intact, and the rest isThe part coating is kept complete, and no defects such as cracking, tilting or peeling are generated.

Description

High-energy laser ablation resistant composite protective coating and preparation method thereof
Technical Field
The invention belongs to the technical field of high-energy laser ablation resistance, relates to a protective coating, and particularly relates to a composite protective coating resistant to high-energy laser ablation and a preparation method thereof.
Background
The high-intensity continuous laser has the advantages of good monochromaticity, collimation, high energy density, high brightness and the like, and makes remarkable progress in the field of air defense and missile defense. When laser light is irradiated on the surface of the material, the material has complex physical and chemical actions with the laser light, so that the material is permanently damaged. In the process, when the material is subjected to thermal coupling with laser, the material absorbs a part of laser energy within a certain skin depth, and then the laser energy is conducted or converted inside the material and is consumed. Due to the thermo-mechanical damage caused by the high intensity continuous laser, the target body without any protective measures is easily melted or vaporized rapidly in a very short time, resulting in pits, perforations and even explosions. The light beam battle can be quickly responded, hit with high precision, reconnaissance against satellite and destroy the electronic information system of enemy, and because of the characteristics, the light beam battle can be developed into the main battle weapon of the modern information war in the 21 st century. Due to the technological progress, the laser technology is continuously developed, and the laser weapon has an increasingly wide application prospect in the photoelectric countermeasure. According to the strength design rule of the airplane, the aluminum alloy material is adopted as the shell, and the missile or airplane in flight can be damaged due to the stress action of the missile or airplane as long as the temperature of the shell is increased by 200 ℃. Aiming at the increasing threat of the aircraft in the flying process, the laser ablation resistant coating is coated on the space missile or the aircraft to be an economical and effective laser damage resistant way.
The laser protection technology can protect the critical processes of each stage of the target and the laser, and is mainly divided into three types, namely reflection type protection for reducing energy coupling, high-melting-point ceramic ablation-resistant protection, ablation type protection for improving energy dissipation and the like. The reflective protection for reducing energy coupling mainly utilizes the high reflectivity of metal to protect the substrate material, and is the first application of researchers to the laser protection technology. For example, Milling et al (Milling R W. laser device and measuring system for aircraft [ P ]]US 3986690.) a reflective layer of Al is added under the outer skin of the aircraft to protect the aircraft from laser damage. The American navy also prepares aluminum-containing organic silicon high-temperature coating TTP-28 with a larger reflection coefficient, and plays a role in resisting laser ablation at the high temperature of 650 ℃. However, as laser energy deposits on the metal surface, the temperature of the metal rises and its internal free electrons move into the crystal latticeThe collision probability increases abruptly, resulting in a sharp increase in resistivity, a substantial decrease in reflectivity and thermal conductivity, and finally a deterioration in protective effect. The ablation-resistant protection of the high-melting-point ceramic is to improve the high-temperature resistance of the material and directly prepare a high-temperature-resistant ceramic coating on the protected material. Pourasad et al (Pourasad J, Ehsani N, Valefi Z. oxidation resistance of a SiC-ZrB2coating prepared by a novel pack cementation on SiC-coated graphite[J]Journal of Materials Science,2017,52(3):1639-4The C powder successfully prepares SiC-ZrB at the temperature of 1873K by utilizing in-situ reaction and a novel embedding technology2Coating; zhang et al (Zhang D, HuP, Dong S, et al. Oxidation scanner and adsorption mechanism of Cf/ZrB2-SiC composite fabricated by vibration-assisted slurry impregnation combined with low-temperature hot pressing[J]Corrossion science,2019,161:108181.) SiC-ZrB was successfully prepared using supersonic plasma spraying2Coating with a heat flux density of 2.4MW/m2The ablation experiment was performed with oxyacetylene. The high-temperature resistant materials prepared by the method have the advantages that the appearance changes in the high-temperature oxidation process, but the integral structure of the coating is not damaged, and the high-temperature resistant materials all show excellent high-temperature ablation resistance. However, the method is complex in process and expensive in cost, and the preparation temperature is too high in the process of preparing the coating, so that the method is not suitable for preparing the relevant coating on the aluminum alloy substrate. Research shows that the laser damage mechanism at the present stage is mainly that light energy is converted into heat energy to be deposited on the surface of a material, so that a large amount of heat is dissipated, and the prevention of heat deposition is also an anti-laser ablation idea. Ma et al (Ma C, Ma Z, Gao L.H, et al, abstract properties of calcium carbonate-filtered phenolic matrix composite coated with irradiated by high energy continuous-wave laser J]Science of advanced materials,2019,11(12): 1712-. But the coating of the dots prepared by the method cannot bear moreHigh energy density laser radiation and the back surface temperature is still maintained at a high level.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to explore a composite coating which is prepared at a low temperature and has excellent high-energy laser ablation resistance, the composite protective coating for resisting high-energy laser ablation has a structure of three-dimensional micropores with the size of 5-20 mu m, and the coating can effectively resist 7kW/cm2After laser irradiation for 10s, the temperature of the back surface of the substrate is obviously lower than the temperature of aging heat treatment, the substrate at the light irradiation center is intact, the coating is kept intact, and defects such as cracking, tilting or peeling are generated.
In order to achieve the above object, the present invention provides a composite protective coating resistant to high-energy laser ablation, which has the following characteristics: the composite protective coating is prepared from silicon carbide whiskers, zirconium diboride powder and zirconia sol, wherein the mass concentration of the zirconia sol is 20-30%, the silicon carbide whiskers account for 10-25%, the zirconium diboride powder accounts for 20-40%, and the zirconia sol accounts for 45-55% in total.
Further, the invention provides a composite protective coating resistant to high-energy laser ablation, and can also have the following characteristics: wherein the diameter of the silicon carbide whisker is 0.1-3.0 μm, and the length is 10-60 μm.
Further, the invention provides a composite protective coating resistant to high-energy laser ablation, and can also have the following characteristics: wherein the particle size of the zirconium diboride powder is 5-10 μm.
Further, the invention provides a composite protective coating resistant to high-energy laser ablation, and can also have the following characteristics: wherein the thickness of the composite protective coating is 1.5-2.5 mm.
The invention also provides a preparation method of the composite protective coating resistant to high-energy laser ablation, which is characterized in that: the method comprises the following steps:
firstly, carrying out surface modification on a substrate polished by abrasive paper by using an ethanol solution of a silane coupling agent;
secondly, surface modification is respectively carried out on the silicon carbide whisker and the zirconium diboride powder by using an ethanol solution of a silane coupling agent;
step three, mixing the modified silicon carbide whiskers and the zirconium diboride powder obtained in the step two with zirconia sol, and stirring until the mixture is uniform to obtain a composite coating;
and step four, coating the composite coating obtained in the step three on the substrate treated in the step one, drying and curing, repeating the operation until the required coating thickness is reached, naturally cooling the coating to room temperature, and obtaining the composite protective coating resistant to high-energy laser ablation on the substrate.
Further, the invention provides a preparation method of the composite protective coating resistant to high-energy laser ablation, and the composite protective coating also has the following characteristics: wherein, in the fourth step, the drying and curing adopts a three-time stepped cooling and delayed curing process, which comprises the following steps: the mixture is put at 70-80 ℃ and kept warm for 10-20 min, then put at 40-60 ℃ and kept warm for 20-40 min, and finally put at 30-40 ℃ and kept warm for 50-70 min.
Further, the invention provides a preparation method of the composite protective coating resistant to high-energy laser ablation, and the composite protective coating also has the following characteristics: and in the fourth step, the thickness of the composite coating in each brushing is controlled within 1 mm.
Further, the invention provides a preparation method of the composite protective coating resistant to high-energy laser ablation, and the composite protective coating also has the following characteristics: wherein, the specific method for modification in the step two is as follows: putting silicon carbide whisker or zirconium diboride powder into a silane coupling agent ethanol solution with the mass fraction of 0.5-1.5%, stirring for 2-3 h in a constant-temperature water bath kettle at the temperature of 60 ℃, and then carrying out suction filtration, drying, grinding and dispersion.
Further, the invention provides a preparation method of the composite protective coating resistant to high-energy laser ablation, and the composite protective coating also has the following characteristics: the third step is specifically as follows: adding the modified silicon carbide whiskers into zirconia sol, and uniformly stirring for 10-20 min to obtain a mixture; adding the modified zirconium diboride powder into the mixture, and continuously stirring until a uniform and viscous composite coating is obtained.
Further, the invention provides a preparation method of the composite protective coating resistant to high-energy laser ablation, and the composite protective coating also has the following characteristics: the specific method for modification in the first step comprises the following steps: soaking the aluminum alloy substrate for 20-40 min by using a silane coupling agent ethanol solution with the mass fraction of 5-10%, then taking out, drying the surface, and then putting the aluminum alloy substrate into an oven at the temperature of 180-220 ℃ for drying for 50-70 min.
Further, the invention provides a preparation method of the composite protective coating resistant to high-energy laser ablation, and the composite protective coating also has the following characteristics: wherein, in the first step and the second step, the silane coupling agent is KH550 or KH 570.
The invention has the beneficial effects that:
the invention relates to a composite coating capable of resisting high-energy laser ablation, which takes zirconia sol as a binder to prepare a laser high-energy laser ablation-resistant composite coating taking diboron zirconium particles and silicon carbide whiskers as main components. The zirconia sol not only acts as a binder and a film-forming agent, but also more importantly, generates high-temperature-resistant ZrO after oxidative decomposition2Ceramic particles. Liquid ZrO during early stages of laser ablation of coatings2-SiO2Self-healing effect of layer and B2O3The volatilization of the compound plays a main role in resisting laser ablation. ZrO with prolonged ablation time2Gel and ZrB2ZrO of filler pyrolysis products2The ceramic barrier layer is gradually protruded in maintaining good laser ablation property, and ZrO2The ceramic barrier layer plays the most important role in resisting laser ablation around the ablation pits.
Secondly, the composite coating which is prepared by the invention and resists the high-energy laser ablation has a spatial net-shaped three-dimensional structure with special points, and the structure is formed by ZrB2ZrO in space of particles and SiC whiskers2The sol is formed under the bonding action. Micron-sized pores (less than or equal to 10 mu m) are uniformly distributed in the composite coating, so that a flowing channel is provided for a liquid ceramic phase in the laser ablation process, and the possibility is provided for further improving the high-temperature ablation resistance of the coating in the later period.
The three-dimensional hole structure of the composite coating resistant to high-energy laser ablation prepared by the invention is beneficial to compensating the thermal expansion of the coating caused by high-energy laser input and slowly releasing the thermal stress, so that the thermal crack in the coating is avoided.
Fourthly, the composite protective coating capable of resisting high-energy laser ablation provided by the invention can effectively resist 7kW/cm2The laser irradiation is carried out for 10s, the substrate at the light irradiation center is intact, and the coating is kept intact without generating defects such as cracking, tilting or peeling.
And fifthly, the high-energy laser ablation resistant coating provided by the invention has excellent laser ablation resistance, and after 10s laser irradiation, the temperature of the back surface of the aluminum alloy substrate is only 171 ℃, which is greatly lower than the aging temperature (200 ℃) of the aluminum alloy substrate.
The composite coating resistant to high-energy laser ablation has the advantages of low preparation temperature, simple process, low cost, good process stability and high repeatability, can be directly brushed on the surface of a protected base material, is suitable for the surface of materials such as aviation aluminum and steel, and can meet the requirement of high-energy continuous laser protection.
Drawings
FIG. 1 is a coating macro-topography provided using example 1 of the present invention;
FIG. 2 is a (500-fold) microscopic profile of a coating provided by example 1 of the present invention;
FIG. 3 is a coating cross-sectional micro-topography (60X) provided using example 1 of the present invention;
FIG. 4 is a coating microtopography (3000 times) provided using example 1 of the present invention;
FIG. 5 is a (12-fold) topographical view of a coating ablated using example 1 of the present invention;
figure 6 is an XRD pattern before and after laser ablation using a coating provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to specific examples. The description examples are only a part of examples, not all examples, and other examples based on the premise of the present invention belong to the protection scope of the present invention.
In the following examples, various starting materials were used, and unless otherwise specified, they were conventional commercially available products.
Example 1
The embodiment provides a composite protective coating resistant to high-energy laser ablation, which is prepared from 10% of silicon carbide whiskers, 40% of zirconium diboride powder, 50% of zirconia sol and 20% -30% of zirconia sol by mass.
The diameter of the SiC whisker is about 1.5 μm, and the length is about 40 μm; the particle size of the zirconium diboride powder was 5 μm.
The preparation method of the composite protective coating resistant to high-energy laser ablation comprises the following steps:
step one, carrying out surface modification on the substrate polished by the sand paper by using an ethanol solution of a silane coupling agent. Specifically, a silane coupling agent ethanol solution with the mass fraction of 8% is used for soaking the aluminum alloy substrate which is polished by the sand paper for 30min, then the aluminum alloy substrate is taken out, and the aluminum alloy substrate is placed into a 200 ℃ drying oven for drying for 60min after the surface is dried;
and secondly, respectively carrying out surface modification on the silicon carbide whisker and the zirconium diboride powder by using an ethanol solution of a silane coupling agent. Specifically, the silicon carbide whisker/zirconium diboride powder is put into a KH550 silane coupling agent ethanol solution with the mass fraction of 1%, stirred in a constant-temperature water bath kettle at the temperature of 60 ℃ for 2 hours, and then subjected to suction filtration, drying, grinding and dispersion. In this embodiment, the KH550 silane coupling agent may be a KH570 silane coupling agent.
And step three, mixing the modified silicon carbide whiskers and the zirconium diboride powder obtained in the step two with zirconia sol, and stirring until the mixture is uniform to obtain the composite coating. Specifically, 1g of modified SiC whisker and 5g of zirconia sol binder are mixed, and are uniformly stirred for 10min to obtain a mixture; weighing the modified 4g ZrB2The powder and mixture were stirred continuously until a homogeneous and viscous composite coating was obtained.
And step four, coating the composite coating obtained in the step three on the substrate treated in the step one, drying and curing, and repeating the operations until the required coating thickness is reached to obtain the composite protective coating resistant to high-energy laser ablation on the substrate. Specifically, coating the composite coating on the aluminum alloy substrate treated in the step one, and putting the substrate coated with the composite coating into a drying oven for drying and curing, wherein the specific steps of drying and curing are as follows: the substrate coated with the composite coating is placed at 80 ℃ and kept warm for 15min, then placed at 50 ℃ and kept warm for 30min, and finally placed at 30 ℃ and kept warm for 60 min. Because the coating is seriously cracked due to the fact that the thickness of the coating is large in one-time coating, multiple times of brushing are adopted, and the thickness of each brushing is controlled within 1 mm. And repeating the coating operation and the drying and curing process until the required coating reaches the required thickness. And naturally cooling the coating to room temperature, and finally obtaining the high-energy laser ablation resistant composite coating on the aluminum alloy substrate. In this example, a coating sample having a thickness of about 2mm was obtained by 3 times of the brushing and curing process.
The porosity of the composite coating resistant to high-energy laser ablation prepared in the embodiment is 10%, and the pore size is 9 μm.
The physical diagram of the composite coating resistant to high-energy laser ablation prepared in this example is shown in fig. 1, which shows a flat surface and no cracks.
The microstructure of the composite coating resistant to high-energy laser ablation prepared in this example is shown in fig. 2 and 4, and it can be observed that the composite coating is formed by ZrB2The particles and the SiC whiskers form a three-dimensional skeleton structure in space under the bonding action of the zirconia sol. ZrB2The surfaces of the particles are coated with zirconium gel, and the silicon carbide whiskers are uniformly dispersed in the coating structure. FIG. 3 is a cross-sectional micro-topography of the composite coating prepared in this example and resistant to high-energy laser ablation, wherein a coating thickness of about 2mm is observed, and no cracks or delamination phenomena are observed in the cross-section.
FIG. 5 shows that the laser energy density of the composite coating prepared in this example is 7.0kW/cm2The microscopic topography after 10s of laser continuous irradiation. The experiment adopts a continuous fiber laser as the laser, the highest output power is 6kW, the diameter of a laser spot is 3mm, and the laser spot is coated on a substrate coated with a high-energy laser ablation resistant coatingA circular spot is formed. The wavelength emitted by the fiber laser is 1060 nm. After high-energy continuous laser irradiation, a typical crater shape is observed in the ablated area of the surface of the composite coating, and the rest of the coating is not peeled off or cracked. In addition, the coating did not peel off from the aluminum alloy substrate surface, indicating that the coating had good laser ablation resistance.
FIG. 6 is an XRD pattern of the composite coating prepared in this example before and after ablation for resisting high-energy laser ablation. The coating can be observed at 7kW/cm2After 10s of irradiation, the phase structure of the coating changed significantly. SiC whisker and ZrB2The powder undergoes an oxidation reaction.
Example 2
The embodiment provides a composite protective coating resistant to high-energy laser ablation, which is prepared from 15% of silicon carbide whiskers, 35% of zirconium diboride powder, 50% of zirconia sol and 20% -30% of zirconia sol by mass.
The diameter of the SiC whisker is about 0.1 μm, and the length of the SiC whisker is about 10 μm; the particle size of the zirconium diboride powder was 10 μm.
The preparation method of the composite protective coating resistant to high-energy laser ablation has the specific operation steps and process parameters basically the same as those of the embodiment 1, and the difference is that the preparation method comprises the following steps:
in the third step, 1.5g of SiC whiskers modified in the second step are mixed with 5g of zirconia sol binder, and the mixture is obtained after uniform stirring for 15 min; weighing the 3.5gZrB modified in the second step2The powder and mixture were stirred continuously until a homogeneous and viscous composite coating was obtained.
In the fourth step, the concrete steps of drying and curing are as follows: the substrate coated with the coating is placed at 70 ℃ and kept warm for 10min, then placed at 40 ℃ and kept warm for 20min, and finally placed at 30 ℃ and kept warm for 50 min. In this example, a coating sample having a thickness of about 2mm was obtained by 3 times of the brushing and curing process.
The porosity of the composite coating resistant to high-energy laser ablation prepared in the embodiment is 15%, and the pore size is 5 μm.
The composite coating prepared by the embodiment and resistant to high-energy laser ablation has the laser energy density of 6.3kW/cm2After the laser continuous irradiation for 10s, the temperature of the back surface of the substrate coated with the high-energy laser ablation resistant coating is 162 ℃.
Example 3
The embodiment provides a composite protective coating resistant to high-energy laser ablation, which is prepared from 20% of silicon carbide whiskers, 35% of zirconium diboride powder, 45% of zirconia sol and 20% -30% of zirconia sol by mass.
The diameter of the SiC whisker is about 2.0 μm, and the length is about 40 μm; the particle size of the zirconium diboride powder was 5 μm.
The preparation method of the composite protective coating resistant to high-energy laser ablation has the specific operation steps and process parameters basically the same as those of the embodiment 1, and the difference is that the preparation method comprises the following steps:
in the first step, the aluminum alloy substrate is soaked in a silane coupling agent ethanol solution with the mass fraction of 5% for 20min, then taken out, dried on the surface, and then placed in an oven at 180 ℃ for drying for 50 min.
And in the second step, stirring 0.5 mass percent ethanol solution of the KH550 silane coupling agent in a constant-temperature water bath kettle at 60 ℃ for 3 hours, and then carrying out suction filtration, drying, grinding and dispersion.
In the third step, 2.0g of SiC whiskers modified in the second step are mixed with 4.5g of zirconia sol binder, and the mixture is obtained after uniform stirring for 20 min; weighing the 3.5gZrB modified in the second step2The powder and mixture were stirred continuously until a homogeneous and viscous composite coating was obtained.
In the fourth step, the concrete steps of drying and curing are as follows: the substrate coated with the coating is placed at 80 ℃ and kept warm for 20min, then placed at 60 ℃ and kept warm for 40min, and finally placed at 40 ℃ and kept warm for 70 min. In this example, a coating sample having a thickness of about 1.5mm was obtained by 2 brushing and curing processes.
The composite coating prepared in this example, which resists high-energy laser ablation, had a porosity of 17% and a pore size of 15 μm.
The composite coating prepared by the embodiment and resistant to high-energy laser ablation has the laser energy density of 4.9kW/cm2After the laser continuous irradiation for 10s, the temperature of the back surface of the substrate coated with the high-energy laser ablation resistant coating is 150 ℃.
Example 4
The embodiment provides a composite protective coating resistant to high-energy laser ablation, which is prepared from 25% of silicon carbide whiskers, 20% of zirconium diboride powder, 55% of zirconia sol and 20% -30% of zirconia sol by mass.
The diameter of the SiC whisker is about 3.0 μm, and the length of the SiC whisker is about 60 μm; the particle size of the zirconium diboride powder was 5 μm.
The preparation method of the composite protective coating resistant to high-energy laser ablation has the specific operation steps and process parameters basically the same as those of the embodiment 1, and the difference is that the preparation method comprises the following steps:
in the first step, the aluminum alloy substrate is soaked in a silane coupling agent ethanol solution with the mass fraction of 10% for 40min, then taken out, dried on the surface, and then placed in a 220 ℃ oven for drying for 70 min.
And in the second step, stirring the ethanol solution of the KH550 silane coupling agent with the mass fraction of 1.5% in a constant-temperature water bath kettle at the temperature of 60 ℃ for 2 hours, and then carrying out suction filtration, drying, grinding and dispersion.
In the third step, 2.5g of SiC whiskers modified in the second step are mixed with 5.5g of zirconia sol binder, and the mixture is obtained after uniform stirring for 20 min; weighing the 2.0gZrB modified in the second step2The powder and mixture were stirred continuously until a homogeneous and viscous composite coating was obtained.
In the fourth step, the concrete steps of drying and curing are as follows: the substrate coated with the coating is placed at 80 ℃ and kept warm for 15min, then placed at 60 ℃ and kept warm for 30min, and finally placed at 30 ℃ and kept warm for 60 min. In this example, a coating sample having a thickness of about 2.5mm was obtained by a 4-pass brushing and curing process.
The porosity of the composite coating resistant to high-energy laser ablation prepared in the embodiment is 20%, and the pore size is 20 μm.
The composite coating prepared by the embodiment and resistant to high-energy laser ablation has the laser energy density of 5.6kW/cm2After the laser continuous irradiation for 10s, the temperature of the back surface of the substrate coated with the high-energy laser ablation resistant coating is 140 ℃.
The above description is only the best mode for carrying out the present invention, and the scope of the present invention is not limited to the above examples. However, all technical solutions that fall under the spirit of the present invention are covered by the scope of the present invention, and any changes and related substitutions that may occur to those skilled in the art within the technical scope of the present invention should be covered by the scope of the present invention.
Parts of the invention not described in detail are within the common general knowledge of a person skilled in the art.

Claims (10)

1. The utility model provides an anti high energy laser ablation's compound protective coating which characterized in that:
the composite protective coating is prepared from silicon carbide whiskers, zirconium diboride powder and zirconia sol, wherein the mass concentration of the zirconia sol is 20-30%, the silicon carbide whiskers account for 10-25%, the zirconium diboride powder accounts for 20-40%, and the zirconia sol accounts for 45-55% in total.
2. The high-energy laser ablation resistant composite protective coating of claim 1, wherein:
wherein the diameter of the silicon carbide whisker is 0.1-3.0 μm, and the length is 10-60 μm.
3. The high-energy laser ablation resistant composite protective coating of claim 1, wherein:
wherein the particle size of the zirconium diboride powder is 5-10 μm.
4. The high-energy laser ablation resistant composite protective coating of claim 1, wherein:
wherein the thickness of the composite protective coating is 1.5-2.5 mm.
5. The method for preparing the high-energy laser ablation resistant composite protective coating according to any one of claims 1 to 4, characterized in that:
the method comprises the following steps:
step one, carrying out surface modification on the polished substrate by using an ethanol solution of a silane coupling agent;
secondly, surface modification is respectively carried out on the silicon carbide whisker and the zirconium diboride powder by using an ethanol solution of a silane coupling agent;
step three, mixing the modified silicon carbide whiskers and the zirconium diboride powder obtained in the step two with zirconia sol, and stirring until the mixture is uniform to obtain a composite coating;
and step four, coating the composite coating obtained in the step three on the substrate treated in the step one, drying and curing, and repeating the operations until the required coating thickness is reached to obtain the composite protective coating resistant to high-energy laser ablation on the substrate.
6. The method for preparing the high-energy laser ablation resistant composite protective coating according to claim 5, characterized in that:
wherein, in the fourth step, the drying and curing adopts a three-time stepped cooling and delayed curing process, which comprises the following steps: the mixture is put at 70-80 ℃ and kept warm for 10-20 min, then put at 40-60 ℃ and kept warm for 20-40 min, and finally put at 30-40 ℃ and kept warm for 50-70 min.
7. The method for preparing the high-energy laser ablation resistant composite protective coating according to claim 5, characterized in that:
and in the fourth step, the thickness of the composite coating in each brushing is controlled within 1 mm.
8. The method for preparing the high-energy laser ablation resistant composite protective coating according to claim 5, characterized in that:
wherein, the specific method for modification in the step two is as follows: putting silicon carbide whisker or zirconium diboride powder into a silane coupling agent ethanol solution with the mass fraction of 0.5-1.5%, stirring for 2-3 h in a constant-temperature water bath kettle at the temperature of 60 ℃, and then carrying out suction filtration, drying, grinding and dispersion.
9. The method for preparing the high-energy laser ablation resistant composite protective coating according to claim 5, characterized in that:
the third step is specifically as follows: adding the modified silicon carbide whiskers into zirconia sol, and uniformly stirring for 10-20 min to obtain a mixture; adding the modified zirconium diboride powder into the mixture, and continuously stirring until a uniform and viscous composite coating is obtained.
10. The method for preparing the high-energy laser ablation resistant composite protective coating according to claim 5, characterized in that:
the specific method for modification in the first step comprises the following steps: soaking the aluminum alloy substrate for 20-40 min by using a silane coupling agent ethanol solution with the mass fraction of 5-10%, then taking out, drying the surface, and then putting the aluminum alloy substrate into an oven at the temperature of 180-220 ℃ for drying for 50-70 min.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050051057A1 (en) * 2003-09-09 2005-03-10 Evans Timothy O. Thermal protective coating for ceramic surfaces
US20050143251A1 (en) * 2002-07-30 2005-06-30 Mehrotra Pankaj K. Ceramic body reinforced with coarse silicon carbide whiskers and method for making the same
CN102060554A (en) * 2010-11-30 2011-05-18 哈尔滨工业大学 High-strength high-toughness zirconium diboride-silicon carbide-zirconia ceramic-based composite material and preparation method thereof
CN103422046A (en) * 2013-08-20 2013-12-04 航天材料及工艺研究所 Preparation method of zirconium diboride and silicon carbide high-temperature antioxidant coating
CN103922745A (en) * 2014-04-03 2014-07-16 西北工业大学 SiC nanowire toughened high temperature ablation resistant ZrB2-SiC composite coating and preparation method thereof
CN111153701A (en) * 2020-01-06 2020-05-15 哈尔滨理工大学 ZrB2-SiC composite coating and preparation method thereof
CN111500146A (en) * 2020-03-11 2020-08-07 中国船舶重工集团公司第七二五研究所 Composite laser ablation resistant coating, preparation method and use method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050143251A1 (en) * 2002-07-30 2005-06-30 Mehrotra Pankaj K. Ceramic body reinforced with coarse silicon carbide whiskers and method for making the same
US20050051057A1 (en) * 2003-09-09 2005-03-10 Evans Timothy O. Thermal protective coating for ceramic surfaces
CN102060554A (en) * 2010-11-30 2011-05-18 哈尔滨工业大学 High-strength high-toughness zirconium diboride-silicon carbide-zirconia ceramic-based composite material and preparation method thereof
CN103422046A (en) * 2013-08-20 2013-12-04 航天材料及工艺研究所 Preparation method of zirconium diboride and silicon carbide high-temperature antioxidant coating
CN103922745A (en) * 2014-04-03 2014-07-16 西北工业大学 SiC nanowire toughened high temperature ablation resistant ZrB2-SiC composite coating and preparation method thereof
CN111153701A (en) * 2020-01-06 2020-05-15 哈尔滨理工大学 ZrB2-SiC composite coating and preparation method thereof
CN111500146A (en) * 2020-03-11 2020-08-07 中国船舶重工集团公司第七二五研究所 Composite laser ablation resistant coating, preparation method and use method thereof

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