A radiation energy absorbing coating for laser and its preparation method

Abstract

The present invention provides a laser radiation energy-absorbing coating and a preparation method thereof, which belongs to the technical field of coating compositions, comprising the following steps: dispersing hexagonal boron nitride powder and glycine in deionized water, ultrasonically treating, ball-milling under inert gas, centrifuging, filtering, washing, and drying to obtain glycine-modified boron nitride; adding graphene oxide to deionized water, ultrasonically treating, adding a layered MoS2 suspension to mix, ultrasonically treating, adding cerium nitrate hexahydrate and ammonia water under magnetic stirring, reacting at high temperature, centrifuging, washing, and drying to obtain CeO2-MoS2 / graphene material; after dispersing CeO2-MoS2 / graphene material, auxiliary agent, anhydrous ethanol, glycine-modified boron nitride, other auxiliary agents, and water, plasma spraying is used on a pretreated copper sheet to deposit a laser radiation energy-absorbing coating. The present invention can achieve high light absorptivity while having certain heat insulation and heat dissipation capabilities.

Description

Technical Field

[0001] The present invention relates to the technical field of coating compositions, and in particular to a radiation energy-absorbing coating for lasers and a preparation method thereof. Background Art

[0002] With the rapid development of industrial manufacturing, aerospace, and defense science and technology, the application scope of high-power lasers continues to expand. In industrial production processes, to improve production efficiency, lasers are often operated continuously at high power. However, the demand for laser beams in production is often intermittent. During periods when laser energy is not needed, a reflector is generally used to direct the laser light to an energy absorption device, converting it into heat energy. The heat is then removed from the system through air or water cooling.

[0003] Existing laser energy absorption devices can be broadly categorized into two types: mechanical and coating-based. Mechanical devices utilize complex structural designs to gradually disperse the laser light through multiple reflections, relying on the metal surface to gradually dissipate the laser energy, thus preventing excessive energy from being concentrated at a single point. Another approach involves applying a radiation-absorbing coating to the laser energy absorption device. This coating utilizes a special coating material that directly absorbs and converts the laser energy. Compared to the complex structural designs required for mechanical devices, coating-based devices are more widely developed and used due to their simplicity.

[0004] However, most existing laser radiation energy-absorbing coatings are expensive and limited to low- to medium-power UV lasers or lasers in other wavelength bands. They cannot withstand long-term high-power UV laser output. Furthermore, over time, the coating absorbs laser energy and converts it into heat, which can cause the laser energy absorption device to melt due to excessive heat, leading to serious safety accidents. Therefore, the design of laser radiation energy-absorbing coatings must not only meet the requirements of laser energy conversion but also provide efficient heat dissipation.

[0005] Therefore, it is necessary to provide a radiation energy absorbing coating for laser and a preparation method thereof to solve the problems existing in the above-mentioned prior art. Summary of the Invention

[0006] In view of this, the present invention provides a radiation energy-absorbing coating for lasers and a preparation method thereof, which can achieve high light absorption rate while having certain heat insulation and heat dissipation capabilities.

[0007] To achieve the above object, the present invention provides a method for preparing a radiation energy-absorbing coating for a laser, comprising the following steps:

[0008] S1. Dispersing hexagonal boron nitride powder and glycine in deionized water, ultrasonically treating, ball milling under inert gas, centrifuging, filtering, washing, and drying to obtain glycine-modified boron nitride;

[0009] S2. adding graphene oxide to deionized water, ultrasonically treating the mixture, adding a layered MoS2 suspension and mixing the mixture, ultrasonically treating the mixture, adding cerium nitrate hexahydrate and ammonia water under magnetic stirring, reacting the mixture at a high temperature, centrifuging the mixture, washing the mixture, and drying the mixture to obtain a CeO2-MoS2 / graphene material;

[0010] S3. Add CeO2-MoS2 / graphene material and additives to anhydrous ethanol, mix and stir, add glycine-modified boron nitride, other additives and water dispersion, and then use plasma spraying on the pretreated copper sheet to deposit a radiation energy-absorbing coating for laser.

[0011] The present invention prepares glycine-modified boron nitride as a thermal insulation and heat dissipation material. Through ball milling and glycine modification, the boron nitride is exfoliated and surface functionalized. Due to its high aspect ratio and surface energy, boron nitride tends to aggregate in a matrix through strong van der Waals interactions between nanosheets. After exfoliation through ball milling, the nitrogen atoms and hydrophilic carboxyl groups in glycine form covalent bonds with the boron atoms in the boron nitride, allowing the highly hydrophilic glycine to adhere to the boron nitride surface, thereby improving its dispersibility in water. This further reduces the thermal interface resistance between the filler and the matrix, enhancing heat conduction at the interface and improving overall heat dissipation performance. Furthermore, because boron nitride itself has a certain degree of thermal insulation, it not only diffuses heat in the matrix but also serves as a thermal barrier.

[0012] The present invention synthesizes CeO2-MoS2 / graphene material by hydrothermal method, wherein graphene oxide is reduced and used as a carrier to load dispersed flaky MoS2 and CeO2 nanoparticles to increase the effective specific surface area of ​​the composite material. The obtained CeO2-MoS2 / graphene material realizes multiple laser absorption mechanisms. Among them, the narrow band gap characteristics of MoS2 give it a natural light absorption advantage, the high conductivity and large specific surface area of ​​graphene provide a fast electron transfer channel, and the introduction of CeO2 can not only enhance the light-heat conversion, but also its reversible CeO2 3+ / Ce 4+ The redox properties can also effectively quench active oxygen, protect the material structure, and inhibit the oxidative degradation of graphene and MoS2. The three synergistically promote interfacial charge separation, extend the carrier lifetime, and thus improve the photothermal conversion efficiency.

[0013] The CeO2-MoS2 / graphene material of the present invention serves as an absorption layer, providing high light absorption and converting laser energy into heat energy, while boron nitride serves as a heat insulation and heat dissipation layer to prevent internal components of the laser from overheating and damage due to absorbing too much energy.

[0014] Optionally, the ultrasonic treatment time in step S1 is 10-20 min, the inert gas is argon, the centrifugal speed is 1200-2000 rpm, the time is 10-15 min, after filtration, it is washed with deionized water 2-3 times, and the drying temperature is 60-70°C for 20-24 h.

[0015] The present invention removes residual hexagonal boron nitride powder by centrifugation and removes excess glycine by washing with deionized water, so that the final product has higher purity.

[0016] Optionally, the ball milling in step S1 is performed in a steel bottle containing zirconia balls with a diameter of 5 mm, the ball milling speed is 400-600 rpm, and the time is 16-24 hours.

[0017] In the ball milling process of the present invention, the boron nitride is subjected to mechanical shearing force in a glycine aqueous solution and is peeled off into a few layers of boron nitride nanosheets, thereby better realizing the modification of the surface thereof.

[0018] Optionally, the layered MoS2 suspension is obtained by immersing molybdenum disulfide in deionized water under a nitrogen environment for 24 to 48 hours, and ultrasonically treating the mixture in a sealed bottle for 1 to 2 hours.

[0019] Optionally, in step S2, graphene oxide is added to deionized water and ultrasonically treated for 1 to 2 hours, a layered MoS2 suspension is added and mixed and ultrasonically treated for 20 to 40 minutes, cerium nitrate hexahydrate and ammonia water are added under magnetic stirring, and the reaction is carried out at 180 to 200°C in a stainless steel hydrothermal synthesis reactor for 12 to 18 hours, centrifuged, washed with distilled water and ethanol 3 to 5 times, and dried at 80 to 120°C for 16 to 24 hours to obtain CeO2-MoS2 / graphene material.

[0020] Optionally, the auxiliary agent is one of aluminum dihydrogen phosphate, aluminum phosphate, and aluminum metaphosphate; the other auxiliary agent is polyacrylic acid or polyvinyl alcohol.

[0021] The present invention uses one of aluminum dihydrogen phosphate, aluminum phosphate, and aluminum metaphosphate as a crosslinking agent to enhance the bonding strength between the coating and the substrate; polyacrylic acid or polyvinyl alcohol is used as a dispersant to keep the mixed liquid stable during the spraying process and prevent material precipitation or stratification.

[0022] Optionally, in step S3, a samarium oxide suspension is also added when adding glycine-modified boron nitride, other additives and water; the samarium oxide suspension is obtained by ball-milling samarium oxide at a speed of 600 rpm for 20 to 40 minutes, adding the resulting mixture to deionized water, and ultrasonically dispersing the mixture for 30 to 50 minutes.

[0023] The present invention also adds a samarium oxide suspension during the preparation of the radiation energy-absorbing coating for the laser. The samarium oxide is pretreated by ball milling and ultrasonic dispersion to refine the samarium oxide particles while helping to evenly disperse the samarium oxide into the solution, ensuring that the material can be evenly adhered to the surface of the copper sheet during the subsequent spraying process. Samarium oxide has a high emissivity and can quickly radiate heat to the outside at a higher temperature, thereby avoiding heat accumulation on the material surface, achieving a heat dissipation effect, and giving the overall coating ablation resistance.

[0024] Optionally, the mixing and stirring time in step S3 is 5~8h, the dispersion time is 20~40min, the plasma spraying current is 600~800A, the main gas argon flow rate is 25~40L / min, the secondary gas hydrogen flow rate is 0.2~0.5L / min, the spraying distance is 6~10mm, the feeding rate is 80~150mL / min, and the coating spraying times are 10~15 times.

[0025] Optionally, the pretreated copper sheet is obtained by ultrasonically cleaning with acetone, ethanol and deionized water in sequence for 5 to 10 minutes.

[0026] The present invention pre-treats the copper sheet to ensure that the surface is clean and free of pollution.

[0027] Optionally, the radiation energy-absorbing coating for laser includes the following raw materials in parts by mass: 60 to 80 parts of CeO2-MoS2 / graphene material, 10 to 15 parts of auxiliary agent, 63.12 to 78.9 parts of anhydrous ethanol, 10 to 15 parts of other auxiliary agents, 3 to 5 parts of glycine-modified boron nitride, and 700 to 900 parts of deionized water.

[0028] The radiation energy-absorbing coating for lasers prepared under the mass ratio of the present invention can achieve good absorptivity and heat insulation and heat dissipation capabilities.

[0029] The above technical solution of the present invention includes at least the following beneficial effects:

[0030] 1. The present invention realizes the surface functionalization of boron nitride through glycine modification. The nitrogen atoms and carboxyl groups in glycine form covalent bonds with the surface of boron nitride, thereby enhancing the dispersibility of boron nitride in water. In addition, boron nitride can effectively realize heat diffusion and provide good thermal insulation performance.

[0031] 2. This invention synthesizes CeO2-MoS2 / graphene materials via a hydrothermal method. Reduced graphene oxide serves as a carrier for flaky MoS2 and CeO2 nanoparticles, increasing the specific surface area of ​​the composite. The narrow bandgap of MoS2 facilitates light absorption, while the high conductivity of graphene accelerates electron transfer. The introduction of CeO2 enhances photothermal conversion and protects the material through a reversible redox reaction, inhibiting oxidation of MoS2 and graphene. The synergistic effect of these three factors improves photothermal conversion efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a graph showing the absorptivity of the sample coating prepared in Example 1 of the present invention in the light energy band of 300-325 nm. DETAILED DESCRIPTION

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are only part of the embodiments of the present invention. All other embodiments obtained by ordinary technicians in this field based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0034] Example 1

[0035] 20 g of hexagonal boron nitride powder and 60 g of glycine were dispersed in 300 mL of deionized water and ultrasonically treated for 20 min. The mixture was then transferred to a steel bottle containing zirconia balls with a diameter of 5 mm and ball-milled at 600 rpm in a planetary ball mill at room temperature and argon atmosphere for 24 h. The mixture was then centrifuged at 2000 rpm for 15 min, filtered, washed three times with deionized water, and dried at 70°C for 24 h to obtain glycine-modified boron nitride.

[0036] Under a nitrogen environment, 40g of molybdenum disulfide was immersed in 500mL of deionized water for 48h, and ultrasonically treated in a sealed bottle for 2h to exfoliate it to obtain a layered MoS2 suspension; 40g of graphene oxide was added to 300mL of deionized water, ultrasonically treated for 2h, 200mL of layered MoS2 suspension was added and mixed, and ultrasonically treated for 40min. 15g of cerium nitrate hexahydrate and 25mL of ammonia water were added to the suspension under magnetic stirring. The mixture was then transferred to a stainless steel hydrothermal synthesis reactor, reacted at 200℃ for 18h, centrifuged, washed with distilled water and ethanol 5 times, and dried in a drying oven at 120℃ for 24h to obtain CeO2-MoS2 / graphene material.

[0037] A 4cm×4cm×2mm copper sheet was selected as the substrate, and ultrasonically cleaned with acetone, ethanol and deionized water for 10 minutes in sequence to obtain a pretreated copper sheet; 15g of samarium oxide was placed in a planetary ball mill and ball-milled at 600rpm for 40 minutes, added to 100mL of deionized water, and ultrasonically dispersed for 50 minutes to obtain a samarium oxide suspension; 80g of CeO2-MoS2 / graphene material and 15g of aluminum dihydrogen phosphate were added to 100mL (i.e., 78.9g) of anhydrous ethanol and mixed and stirred for 8h, then 15g of polyacrylic acid, 5g of glycine-modified boron nitride, 80mL of samarium oxide suspension and 900mL of deionized water were added, and dispersed with a cell disruptor for 40 minutes to form a suspension; the suspension was sprayed on the pretreated copper sheet using plasma spraying equipment to deposit a radiation energy-absorbing coating for laser use. The specific parameters of the spraying process using plasma spraying equipment are: spraying current is 800A, main gas argon flow rate is 40L / min, secondary gas hydrogen flow rate is 0.2L / min, spraying distance is 10mm, feeding rate is 80mL / min, and coating spraying times is 15 times.

[0038] Example 2

[0039] 20 g of hexagonal boron nitride powder and 40 g of glycine were dispersed in 300 mL of deionized water and ultrasonically treated for 10 minutes. The mixture was then transferred to a steel bottle containing zirconia balls with a diameter of 5 mm and ball-milled at 400 rpm in a planetary ball mill at room temperature and argon atmosphere for 16 hours. The mixture was then centrifuged at 1200 rpm for 10 minutes, filtered, washed twice with deionized water, and dried at 60°C for 20 hours to obtain glycine-modified boron nitride.

[0040] Under a nitrogen environment, 40g of molybdenum disulfide was immersed in 500mL of deionized water for 24h, and ultrasonically treated in a sealed bottle for 1h to exfoliate it to obtain a layered MoS2 suspension; 20g of graphene oxide was added to 300mL of deionized water, ultrasonically treated for 1h, 200mL of layered MoS2 suspension was added and mixed, and ultrasonically treated for 20min. 10g of cerium nitrate hexahydrate and 20mL of ammonia water were added to the suspension under magnetic stirring, and then the mixture was transferred to a stainless steel hydrothermal synthesis reactor, reacted at 180°C for 12h, centrifuged, washed with distilled water and ethanol 3 times, and dried in a drying oven at 80°C for 16h to obtain CeO2-MoS2 / graphene material.

[0041] A 4cm×4cm×2mm copper sheet was selected as the substrate, and ultrasonically cleaned with acetone, ethanol and deionized water for 5 minutes in sequence to obtain a pretreated copper sheet; 12g of samarium oxide was placed in a planetary ball mill and ball-milled at a speed of 600rpm for 20 minutes, added to 100mL of deionized water, and ultrasonically dispersed for 30 minutes to obtain a samarium oxide suspension; 60g of CeO2-MoS2 / graphene material and 10g of aluminum phosphate were added to 80mL (i.e., 63.12g) of anhydrous ethanol and mixed and stirred for 5 hours, then 10g of polyvinyl alcohol, 3g of glycine-modified boron nitride, 70mL of samarium oxide suspension and 700mL of deionized water were added, and dispersed with a cell crusher for 20 minutes to form a suspension; the suspension was sprayed on the pretreated copper sheet using plasma spraying equipment to deposit an irradiation energy-absorbing coating for lasers. The specific parameters of the spraying process using plasma spraying equipment are: spraying current is 600A, main gas argon flow rate is 25L / min, secondary gas hydrogen flow rate is 0.5L / min, spraying distance is 6mm, feeding rate is 150mL / min, and the number of coating spraying passes is 10 times.

[0042] Example 3

[0043] 20 g of hexagonal boron nitride powder and 50 g of glycine were dispersed in 300 mL of deionized water and ultrasonically treated for 15 minutes. The mixture was then transferred to a steel bottle containing zirconia balls with a diameter of 5 mm and ball-milled at 500 rpm in a planetary ball mill at room temperature and argon atmosphere for 20 hours. The mixture was then centrifuged at 1800 rpm for 12 minutes, filtered, washed twice with deionized water, and dried at 65°C for 22 hours to obtain glycine-modified boron nitride.

[0044] Under a nitrogen environment, 40g of molybdenum disulfide was immersed in 500mL of deionized water for 36h, and ultrasonically treated in a sealed bottle for 1.5h to exfoliate it to obtain a layered MoS2 suspension; 30g of graphene oxide was added to 300mL of deionized water, ultrasonically treated for 1.5h, 200mL of layered MoS2 suspension was added and mixed, and ultrasonically treated for 30min. 12g of cerium nitrate hexahydrate and 22mL of ammonia water were added to the suspension under magnetic stirring. The mixture was then transferred to a stainless steel hydrothermal synthesis reactor, reacted at 190°C for 16h, centrifuged, washed 4 times with distilled water and ethanol, and dried in a drying oven at 110°C for 20h to obtain CeO2-MoS2 / graphene material.

[0045] A 4cm×4cm×2mm copper sheet was selected as the substrate, and ultrasonically cleaned with acetone, ethanol and deionized water for 8 minutes in sequence to obtain a pretreated copper sheet; 13g of samarium oxide was placed in a planetary ball mill and ball-milled at 600rpm for 30 minutes, added to 100mL of deionized water, and ultrasonically dispersed for 40 minutes to obtain a samarium oxide suspension; 70g of CeO2-MoS2 / graphene material and 13g of aluminum metaphosphate were added to 90mL (i.e., 71.01g) of anhydrous ethanol and mixed and stirred for 6 hours, then 12g of polyvinyl alcohol, 4g of glycine-modified boron nitride, 72mL of samarium oxide suspension and 800mL of deionized water were added, and dispersed with a cell crusher for 30 minutes to form a suspension; the suspension was sprayed on the pretreated copper sheet using plasma spraying equipment to deposit a radiation energy-absorbing coating for lasers. The specific parameters of the spraying process using plasma spraying equipment are: spraying current is 700A, main gas argon flow rate is 30L / min, secondary gas hydrogen flow rate is 0.4L / min, spraying distance is 8mm, feeding rate is 90mL / min, and the number of coating spraying times is 14 times.

[0046] Example 4

[0047] 20 g of hexagonal boron nitride powder and 45 g of glycine were dispersed in 300 mL of deionized water and ultrasonically treated for 15 minutes. The mixture was then transferred to a steel bottle containing zirconia balls with a diameter of 5 mm and ball-milled at 500 rpm in a planetary ball mill at room temperature and argon atmosphere for 18 hours. The mixture was then centrifuged at 1600 rpm for 13 minutes, filtered, washed twice with deionized water, and dried at 70°C for 20 hours to obtain glycine-modified boron nitride.

[0048] Under a nitrogen environment, 40g of molybdenum disulfide was immersed in 500mL of deionized water for 40h, and ultrasonically treated in a sealed bottle for 1.5h to exfoliate it to obtain a layered MoS2 suspension; 25g of graphene oxide was added to 300mL of deionized water, ultrasonically treated for 2h, 200mL of layered MoS2 suspension was added and mixed, and ultrasonically treated for 35min. 11g of cerium nitrate hexahydrate and 22mL of ammonia water were added to the suspension under magnetic stirring. The mixture was then transferred to a stainless steel hydrothermal synthesis reactor, reacted at 190°C for 16h, centrifuged, washed 4 times with distilled water and ethanol, and dried in a drying oven at 110°C for 18h to obtain CeO2-MoS2 / graphene material.

[0049] A 4cm×4cm×2mm copper sheet was selected as the substrate, and ultrasonically cleaned with acetone, ethanol and deionized water for 8 minutes in sequence to obtain a pretreated copper sheet; 14g of samarium oxide was placed in a planetary ball mill and ball-milled at 600rpm for 25 minutes, added to 100mL of deionized water, and ultrasonically dispersed for 35 minutes to obtain a samarium oxide suspension; 75g of CeO2-MoS2 / graphene material and 12g of aluminum dihydrogen phosphate were added to 90mL (i.e., 71.01g) of anhydrous ethanol and mixed and stirred for 6 hours, then 12g of polyvinyl alcohol, 4.5g of glycine-modified boron nitride, 75mL of samarium oxide suspension and 750mL of deionized water were added, and dispersed with a cell disruptor for 25 minutes to form a suspension; the suspension was sprayed on the pretreated copper sheet using plasma spraying equipment to deposit a radiation energy-absorbing coating for lasers. The specific parameters of the spraying process using plasma spraying equipment are: spraying current is 800A, main gas argon flow rate is 35L / min, secondary gas hydrogen flow rate is 0.3L / min, spraying distance is 8mm, feeding rate is 120mL / min, and the number of coating spraying times is 13 times.

[0050] Example 5

[0051] 20 g of hexagonal boron nitride powder and 50 g of glycine were dispersed in 300 mL of deionized water and ultrasonically treated for 20 min. The mixture was then transferred to a steel bottle containing zirconia balls with a diameter of 5 mm and ball-milled at 500 rpm in a planetary ball mill at room temperature and argon atmosphere for 22 h. The mixture was then centrifuged at 1800 rpm for 12 min, filtered, washed three times with deionized water, and dried at 65°C for 22 h to obtain glycine-modified boron nitride.

[0052] Under a nitrogen environment, 40g of molybdenum disulfide was immersed in 500mL of deionized water for 48h, and ultrasonically treated in a sealed bottle for 1h to exfoliate it to obtain a layered MoS2 suspension; 20g of graphene oxide was added to 300mL of deionized water, ultrasonically treated for 2h, 200mL of layered MoS2 suspension was added and mixed, and ultrasonically treated for 30min. 12g of cerium nitrate hexahydrate and 23mL of ammonia water were added to the suspension under magnetic stirring. The mixture was then transferred to a stainless steel hydrothermal synthesis reactor, reacted at 200°C for 16h, centrifuged, washed 4 times with distilled water and ethanol, and dried in a drying oven at 100°C for 18h to obtain CeO2-MoS2 / graphene material.

[0053] A 4cm×4cm×2mm copper sheet was used as a substrate and ultrasonically cleaned for 8 minutes using acetone, ethanol, and deionized water, respectively, to obtain a pretreated copper sheet. 70g of CeO₂-MoS₂ / graphene material and 12g of aluminum metaphosphate were added to 90mL (i.e., 71.01g) of anhydrous ethanol and stirred for 6 hours. Then, 12g of polyacrylic acid, 4g of glycine-modified boron nitride, and 800mL of deionized water were added and dispersed using a cell disrupter for 30 minutes to form a suspension. The suspension was then sprayed onto the pretreated copper sheet using a plasma sprayer to deposit a laser radiation energy-absorbing coating. The specific parameters for the plasma spraying process were: spray current 700A, primary argon flow rate 30L / min, secondary hydrogen flow rate 0.4L / min, spray distance 10mm, feed rate 150mL / min, and 12 spray passes.

[0054] Example 6

[0055] 20 g of hexagonal boron nitride powder and 50 g of glycine were dispersed in 300 mL of deionized water and ultrasonically treated for 20 minutes. The mixture was then transferred to a steel bottle containing zirconia balls with a diameter of 5 mm and ball-milled at 500 rpm in a planetary ball mill at room temperature and argon atmosphere for 20 hours. The mixture was then centrifuged at 1800 rpm for 15 minutes, filtered, washed three times with deionized water, and dried at 70°C for 20 hours to obtain glycine-modified boron nitride.

[0056] Under a nitrogen environment, 40g of molybdenum disulfide was immersed in 500mL of deionized water for 24h, and ultrasonically treated in a sealed bottle for 1h to exfoliate it to obtain a layered MoS2 suspension; 40g of graphene oxide was added to 300mL of deionized water, ultrasonically treated for 2h, 200mL of layered MoS2 suspension was added and mixed, and ultrasonically treated for 20min. 12g of cerium nitrate hexahydrate and 25mL of ammonia water were added to the suspension under magnetic stirring. The mixture was then transferred to a stainless steel hydrothermal synthesis reactor, reacted at 180°C for 14h, centrifuged, washed 4 times with distilled water and ethanol, and dried in a drying oven at 110°C for 20h to obtain CeO2-MoS2 / graphene material.

[0057] A 4cm×4cm×2mm copper sheet was selected as the substrate, and ultrasonically cleaned with acetone, ethanol and deionized water for 6 minutes in sequence to obtain a pretreated copper sheet; 12g of samarium oxide was placed in a planetary ball mill and ball-milled at 600rpm for 30 minutes, added to 100mL of deionized water, and ultrasonically dispersed for 50 minutes to obtain a samarium oxide suspension; 70g of CeO2-MoS2 / graphene material and 12g of aluminum phosphate were added to 90mL (i.e., 71.01g) of anhydrous ethanol and mixed and stirred for 7h, then 15g of polyacrylic acid, 5g of glycine-modified boron nitride, 70mL of samarium oxide suspension and 900mL of deionized water were added, and dispersed with a cell crusher for 20 minutes to form a suspension; the suspension was sprayed on the pretreated copper sheet using plasma spraying equipment to deposit a radiation energy-absorbing coating for laser use. The specific parameters of the plasma spraying process are as follows: spraying current is 800A, main gas argon flow rate is 25L / min, secondary gas hydrogen flow rate is 0.5L / min, spraying distance is 8mm, feeding rate is 150mL / min, and coating spraying times is 10 times.

[0058] The present invention also carried out comparative examples and related tests.

[0059] Comparative Example 1

[0060] Compared with Example 1, the only difference is that CeO2-MoS2 / graphene material is not prepared, and MoS2 is directly added. The other components and preparation methods remain unchanged, and finally a radiation energy-absorbing coating for laser is prepared.

[0061] Comparative Example 2

[0062] Compared with Example 1, the only difference is that glycine-modified boron nitride is not prepared, and boron nitride is directly added. The other components and preparation methods remain unchanged, and finally a radiation energy-absorbing coating for laser is prepared.

[0063] Comparative Example 3

[0064] Compared with Example 1, the only difference is that CeO2-MoS2 / graphene material is not prepared, CeO2 nanoparticles and MoS2 are directly added, and the other components and preparation methods remain unchanged. Finally, a radiation energy-absorbing coating for laser is obtained.

[0065] Performance testing

[0066] The performance test analysis of Examples 1 to 6 and Comparative Examples 1 to 3 was carried out, and the ultraviolet light absorption rate performance test was carried out in the 300-325nm band according to the national standard experimental method of GB / T26813-2011. The absorption rate of the sample coating prepared in Example 1 for the light energy in the 300-325nm band was as follows: Figure 1The absorptivity of the sample coatings prepared in Examples 1 to 6 and Comparative Examples 1 to 3 in the 308 nm wavelength band is shown in Table 1.

[0067] The laser tolerance test was performed on the sample coatings prepared in Examples 1 to 6 and Comparative Examples 1 to 3. The specific experimental steps are as follows: after irradiating the sample coating with a 500W high-power 308nm laser for 72 hours, an infrared thermal imager was used to monitor the temperature of the back of the copper substrate in real time, the coating depression depth was measured using a surface profiler, and the coating peeling area ratio was calculated. Finally, the surface temperature, ablation depth and coating peeling rate of the sample coating after irradiation were obtained. The specific test results are shown in Table 1 below.

[0068] Table 1

[0069]

[0070] As can be seen from Table 1, the laser radiation energy-absorbing coatings prepared in Examples 1 to 6 have better absorption rates of light energy in the 308 nm band and perform better in the laser tolerance test than Comparative Examples 1 to 3; the laser tolerance of Example 5 is somewhat reduced due to the fact that no samarium oxide suspension is added to the suspension.

[0071] According to the data analysis in Table 1, compared with Example 1, Comparative Example 1 did not prepare CeO2-MoS2 / graphene material, resulting in a significant decrease in the absorption rate of light energy, and the performance of the coating after laser irradiation was also significantly affected; and Example 1 used glycine to modify boron nitride, which improved its dispersibility so that the temperature of the coating after laser irradiation was diffused and the coating peeling rate was also significantly reduced; Comparative Example 3 did not use graphene loading, which destroyed the synergistic effect and significantly reduced the performance. Figure 1 The sample coating prepared in Example 1 shows the absorption rate of light energy in the 300-325nm band, showing that the absorption rate reaches 95.7% in the 308nm band. In summary, the radiation energy-absorbing coating for lasers prepared in this invention has excellent light absorption and laser tolerance.

[0072] The above is a preferred embodiment of the present invention. Those skilled in the art may make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a radiation energy-absorbing coating for a laser, characterized in that: The steps include: S1. Dispersing hexagonal boron nitride powder and glycine in deionized water, ultrasonically treating, ball milling under inert gas, centrifuging, filtering, washing, and drying to obtain glycine-modified boron nitride; S2. adding graphene oxide to deionized water, ultrasonically treating the mixture, adding a layered MoS2 suspension and mixing the mixture, ultrasonically treating the mixture, adding cerium nitrate hexahydrate and ammonia water under magnetic stirring, reacting the mixture at a high temperature, centrifuging the mixture, washing the mixture, and drying the mixture to obtain a CeO2-MoS2 / graphene material; S3. Add CeO2-MoS2 / graphene material and additives to anhydrous ethanol, mix and stir, add glycine-modified boron nitride, other additives and water dispersion, and then use plasma spraying on the pretreated copper sheet to deposit a radiation energy-absorbing coating for laser.

2. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: In step S1, the ultrasonic treatment time is 10-20 minutes, the inert gas is argon, the centrifugal speed is 1200-2000 rpm, and the time is 10-15 minutes. After filtration, the product is washed with deionized water 2-3 times, and the drying temperature is 60-70° C. and the time is 20-24 hours.

3. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: In step S1, the ball milling is performed in a steel bottle containing zirconia balls with a diameter of 5 mm, with a ball milling speed of 400-600 rpm and a time of 16-24 hours.

4. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: The layered MoS2 suspension is obtained by immersing molybdenum disulfide in deionized water for 24 to 48 hours under a nitrogen environment and ultrasonically treating it in a sealed bottle for 1 to 2 hours.

5. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: In the step S2, graphene oxide is added to deionized water and ultrasonically treated for 1-2 hours, a layered MoS2 suspension is added and mixed and ultrasonically treated for 20-40 minutes, cerium nitrate hexahydrate and ammonia water are added under magnetic stirring, and the reaction is carried out at 180°C-200°C in a stainless steel hydrothermal synthesis reactor for 12-18 hours, followed by centrifugation, washing with distilled water and ethanol for 3-5 times, and drying at 80-120°C for 16-24 hours to obtain a CeO2-MoS2 / graphene material.

6. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: The auxiliary agent is one of aluminum dihydrogen phosphate, aluminum phosphate, and aluminum metaphosphate; the other auxiliary agent is polyacrylic acid or polyvinyl alcohol.

7. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: In step S3, a samarium oxide suspension is added when adding glycine-modified boron nitride, other additives and water; the samarium oxide suspension is obtained by ball milling samarium oxide at a speed of 600 rpm for 20 to 40 minutes, adding it to deionized water, and ultrasonically dispersing it for 30 to 50 minutes.

8. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: The mixing and stirring time in step S3 is 5 to 8 hours, the dispersion time is 20 to 40 minutes, the plasma spraying current is 600 to 800 A, the main gas argon flow rate is 25 to 40 L / min, the secondary gas hydrogen flow rate is 0.2 to 0.5 L / min, the spraying distance is 6 to 10 mm, the feeding rate is 80 to 150 mL / min, and the coating spraying times are 10 to 15 times.

9. The method for preparing a radiation energy absorbing coating for laser according to claim 1, characterized in that: The pretreated copper sheet is obtained by ultrasonically cleaning with acetone, ethanol and deionized water in sequence for 5 to 10 minutes.

10. A radiation energy-absorbing coating for lasers, prepared by the method for preparing a radiation energy-absorbing coating for lasers according to any one of claims 1 to 9, characterized in that: The method comprises the following raw materials in parts by mass: 60-80 parts of CeO2-MoS2 / graphene material, 10-15 parts of auxiliary agent, 63.12-78.9 parts of anhydrous ethanol, 10-15 parts of other auxiliary agents, 3-5 parts of glycine-modified boron nitride, and 700-900 parts of deionized water.

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