Organic silicon resin-based laser protective coating and preparation method thereof
Technical Field
The invention relates to the field of fine chemical engineering, in particular to an organic silicon resin-based laser protective coating and a preparation method thereof.
Background
Laser has been widely used in industry, business, scientific research, medical treatment and military affairs, because of its high brightness, good directivity, not easy to be interfered, and wide frequency band. However, due to the high energy density and concentrated energy of the laser, it may cause great damage to the irradiated part of the human body. With the continuous improvement of laser energy, the continuous increase of laser varieties and the continuous expansion of laser application range, the destructive effect of laser on human vision and equipment is more and more serious, especially infrared laser of 1.06 μm, 1.54 μm, 10.6 μm and the like, so the research on the protection of laser damage is also carried out synchronously. Due to the high energy of the laser, the irradiation on the surface of the material can cause local temperature rise, and the structure of the material can be damaged. In the existing laser protective materials, the research on high-temperature resistant laser protective coating materials is rare. Moreover, the application field of laser is more and more extensive, the application environment of the laser protective coating is more and more diversified, and the research on the laser protective material which can be applied to the low-temperature environment is less.
Disclosure of Invention
The first purpose of the invention is to provide an organic silicon resin-based laser protection coating, which has absorption and up-conversion effects on infrared laser with the wavelength of 1.06 mu m and 1.54 mu m, has absorption effects on infrared laser with the wavelength of 10.6 mu m, and can achieve the purpose of laser protection. Can bear the temperature change in the range of minus 40 ℃ to 350 ℃, and the diffuse reflectance of the coating is kept below 1 percent.
The second purpose of the invention is to provide a preparation method of the organic silicon resin-based laser protective coating, the method adopts a spraying method to prepare the laser protective coating, the prepared coating can be cured at room temperature, and the coating has the advantages of thin thickness, uniform thickness, good surface state, adhesive force of more than or equal to level 1, impact strength of more than or equal to 50 kg.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
an organosilicon resin-based laser protective coating, the matrix of which is high-temperature resistant self-drying organosilicon resin, and the filler is (Sm)1-x-yErxMny)BO3Wherein x is more than or equal to 0.005 and less than or equal to 0.02, and y is more than or equal to 0.1 and less than or equal to 0.2.
Filler (Sm)1-x-yErxMny)BO3The preparation method adopts a citric acid-nitrate sol-gel combustion synthesis method, and comprises the following steps:
(1) weighing Sm (NO) according to stoichiometric ratio3)3·6H2O、Er(NO3)3·5H2O、Mn(NO3)2·4H2Placing O, boric acid and a certain amount of citric acid in a beaker, adding distilled water, and uniformly stirring to form transparent sol;
(2) sealing the beaker, heating while stirring and refluxing on a constant-temperature magnetic stirrer;
(3) unsealing, continuously heating and stirring on a constant-temperature magnetic stirrer, and continuously evaporating water until transparent gel is formed;
(4) placing the beaker filled with the transparent gel in an electric heating blast drying oven for heat treatment to form fluffy precursor powder;
(5) calcining the precursor powder in a rapid heating box type resistance furnace at a certain temperature in air atmosphere, cooling, and grinding to obtain the filler (Sm)1-x-yErxMny)BO3。
Wherein the mole number of the citric acid in the step (1) is equal to Sm (NO)3)3·6H2O、Er(NO3)3·5H2O、Mn(NO3)2·4H2The ratio of the total molar number of O and boric acid is 1-2.
Wherein the heating temperature in the step (2) is 60-80 ℃, and the refluxing time is 0.5-2 h.
Wherein the heating temperature in the step (3) is 60-80 ℃.
Wherein the heat treatment temperature of the transparent gel in the step (4) is 150-200 ℃, and the heat treatment time is 2-4 h.
Wherein the calcination temperature of the precursor powder in the step (5) is 600-800 ℃, and the heat treatment time is 2-4 h.
A preparation method of an organic silicon resin-based laser protective coating comprises the following steps:
(1) polishing the aluminum plate by 400-600-mesh sand paper for 1-2 min, cleaning and airing;
(2) weighing the organic silicon resin and the filler (Sm)1-x-yErxMny)BO3Adding a diluent, and stirring for 10-15 min;
(3) pouring the mixed coating obtained in the step (2) into a spray gun, wherein the pressure of the spray gun is 1-2 MPa, the distance between a gun opening and an aluminum plate is 10-15 cm, uniformly spraying the mixed coating on the aluminum plate obtained in the step (1) to obtain (Sm)1-x-yErxMny)BO3A silicone resin coating;
(4) spraying (Sm) the spraying material in the step (3)1-x-yErxMny)BO3Curing the aluminum plate with the organic silicon resin coating at room temperature for 20-30 h to obtain the organic silicon resin-based laser protective coating.
In the step (2), the diluent is toluene, and the mass ratio of toluene to the silicone resin is as follows: 1: (6-8); the mass ratio of the filler to the organosilicon matrix is 0.75-1.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides an organic silicon resin-based laser protective coating, which utilizes rare earth Sm3+Is/are as follows6H5/2Ground state of the tube6F9/2Excited transition promoting filler (Sm)1-x-yErxMny)BO3In the wave band range of 1.05-1.15 μm, the infrared laser with the wavelength of 1.06 μm can be absorbed by rare earth Sm3+Is/are as follows6H5/2Ground state of the tube6H13/2Transition sum of excited states Er3+Is/are as follows4I15/2Ground state of the tube4I13/2Excited transition promoting filler (Sm)1-x-yErxMny)BO3Can absorb infrared laser with the wavelength of 1.54 mu m within the range of 1.50-1.65 mu m and utilize (Sm)1-x-yErxMny)BO3Vibration absorption of the middle B-O-B bond and [ BO3]The activated B-O in the triangular body symmetrically expands and contracts to vibrate, and can absorb 10.6 mu m infrared laser, so that the aim of laser protection is fulfilled. Er3+And Mn2+Can enter SmBO3Form (Sm) in the crystal lattice of (1)1-x-yErxMny)BO3Solid solution, Er3+The (Sm) is further enhanced by the inverse Stokes process of upconversion of 1.06 and 1.54 μm infrared laser light to visible light1-x-yErxMny)BO3Laser protection capability of (2); after Mn doping, in (Sm)1-x-yErxMny)BO3The valence change is generated in the process, so that (Sm) is doped1-x-yErxMny)BO3 The carrier concentration in the powder is increased, the absorption of light is integrally improved, and the (Sm) is enhanced again1-x-yErxMny)BO3The laser protection capability is achieved, and therefore the purpose of laser protection is achieved. Adopting high-temperature resistant self-drying organic silicon resin as a matrix, adding citric acid-nitrate sol gel for combustionNanometer (Sm) prepared by sintering synthesis method1-x-yErxMny)BO3The composite coating material prepared from the powder can bear the temperature change within the range of minus 40 ℃ to 350 ℃, the diffuse reflectance of the coating is kept below 1%, and the surface state of the coating is not changed.
(2) According to the preparation method of the organic silicon resin-based laser protective coating, the laser protective coating is prepared by adopting a spraying method, and the prepared coating can be cured at room temperature and has the advantages of thin thickness, uniform thickness, good surface state, high adhesive force, good flexibility, high impact strength and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows the diffuse reflection absorption spectra of the laser protective coating provided in example 1 at 900-1200 nm wavelength range after heat treatment at different temperatures;
FIG. 2 is a graph showing the diffuse reflection absorption spectra of the laser protective coating provided in example 1 at 1300-1650 nm wavelength range after heat treatment at different temperatures;
FIG. 3 is a graph of the upconversion fluorescence spectrum of the laser protective coating material provided in example 2 under excitation of laser with a wavelength of 1.06 μm;
FIG. 4 is a graph of the upconversion fluorescence spectrum of the laser protective coating material provided in example 2 under excitation of laser with a wavelength of 1.54 μm;
FIG. 5 is an FTIR spectrum of fillers in a laser protective coating provided in example 2;
fig. 6 is an XRD pattern of the filler in the laser protective coating provided in example 2.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
An organosilicon resin-based laser protective coating, the matrix of which is high-temperature resistant self-drying organosilicon resin, and the filler is (Sm)0.895Er0.005Mn0.1)BO3The mass ratio of the filler to the matrix is 0.75, and the filler (Sm)0.895Er0.005Mn0.1)BO3The preparation method adopts a citric acid-nitrate sol-gel combustion synthesis method, and comprises the following steps:
(1) weighing 19.917gSm (NO) according to stoichiometric ratio3)3·6H2O、0.111gEr(NO3)3·5H2O、1.257gMn(NO3)2·4H2Placing O, 3.096g of boric acid and 21.041g of citric acid in a beaker, adding distilled water, and uniformly stirring to form transparent sol;
(2) sealing the beaker, heating while stirring and refluxing for 0.5h at 60 ℃ on a constant-temperature magnetic stirrer;
(3) unsealing, continuously heating and stirring at 80 ℃ on a constant-temperature magnetic stirrer, and continuously evaporating water until transparent gel is formed;
(4) placing the beaker filled with the transparent gel into an electric heating forced air drying oven to carry out heat treatment for 4 hours at the temperature of 150 ℃ to form fluffy precursor powder;
(5) calcining the precursor powder in a rapid heating box type resistance furnace at 600 ℃ for 2h in air atmosphere, cooling and grinding to obtain the filler (Sm)0.895Er0.005Mn0.1)BO3。
(Sm0.895Er0.005Mn0.1)BO3The preparation method of the organic silicon resin-based laser protective coating comprises the following steps:
(1) polishing the aluminum plate with 400-mesh sand paper for 1min, cleaning and airing;
(2) weighing 10g of high-temperature resistant self-drying organic silicon resin and 7g of high-temperature resistant self-drying organic silicon resin5g of Filler (Sm)0.895Er0.005Mn0.1)BO3Adding 1.67g of toluene, and stirring for 10 min;
(3) pouring the mixed coating obtained in the step (2) into a spray gun, wherein the pressure of the spray gun is 1MPa, the distance between a gun opening and the aluminum plate is 15cm, and uniformly spraying the mixed coating on the aluminum plate obtained in the step (1) to obtain the (Sm)0.895Er0.005Mn0.1)BO3A silicone resin coating;
(4) spraying (Sm) the spraying material in the step (3)0.895Er0.005Mn0.1)BO3Curing the aluminum plate with the organic silicon resin coating at room temperature for 20 hours to obtain the organic silicon resin-based laser protective coating.
Example 2
An organosilicon resin-based laser protective coating, the matrix of which is high-temperature resistant self-drying organosilicon resin, and the filler is (Sm)0.85Er0.01Mn0.14)BO3The mass ratio of the filler to the matrix is 0.8, and the filler (Sm)0.85Er0.01Mn0.14)BO3The preparation method adopts a citric acid-nitrate sol-gel combustion synthesis method, and comprises the following steps:
(1) weighing 20.296gSm (NO) according to stoichiometric ratio3)3·6H2O、0.113gEr(NO3)3·5H2O、1.281gMn(NO3)2·4H2Placing O, 3.154g of boric acid and 30.018g of citric acid in a beaker, adding distilled water, and uniformly stirring to form transparent sol;
(2) sealing the beaker, and heating and stirring for refluxing for 1h at 70 ℃ on a constant-temperature magnetic stirrer;
(3) unsealing, continuously heating and stirring at 75 ℃ on a constant-temperature magnetic stirrer, and continuously evaporating water until transparent gel is formed;
(4) placing the beaker filled with the transparent gel into an electric heating forced air drying oven to carry out heat treatment for 3 hours at 160 ℃ to form fluffy precursor powder;
(5) placing the precursor powder in a rapid heating box type electric heaterCalcining in a furnace at 700 deg.C for 2.5h in air atmosphere, cooling, and grinding to obtain filler (Sm)0.85Er0.01Mn0.14)BO3。
(Sm0.85Er0.01Mn0.14)BO3The preparation method of the organic silicon resin-based laser protective coating comprises the following steps:
(1) polishing the aluminum plate with 500-mesh sand paper for 1.5min, cleaning and airing;
(2) weighing 10g of high-temperature-resistant self-drying organic silicon resin and 8g of filler (Sm)0.85Er0.01Mn0.14)BO3Adding 1.43g of toluene, and stirring for 12 min;
(3) pouring the mixed coating obtained in the step (2) into a spray gun, wherein the pressure of the spray gun is 1.5MPa, the distance between a gun opening and the aluminum plate is 14cm, and uniformly spraying the mixed coating on the aluminum plate obtained in the step (1) to obtain the (Sm)0.85Er0.01Mn0.14)BO3A silicone resin coating;
(4) spraying (Sm) the spraying material in the step (3)0.85Er0.01Mn0.14)BO3Curing the aluminum plate with the organic silicon resin coating at room temperature for 24 hours to obtain the organic silicon resin-based laser protective coating.
Example 3
An organosilicon resin-based laser protective coating, the matrix of which is high-temperature resistant self-drying organosilicon resin, and the filler is (Sm)0.815Er0.015Mn0.17)BO3The mass ratio of the filler to the matrix is 0.9, filler (Sm)0.815Er0.015Mn0.17)BO3The preparation method adopts a citric acid-nitrate sol-gel combustion synthesis method, and comprises the following steps:
(1) weighing 20.588gSm (NO) according to stoichiometric ratio3)3·6H2O、0.115gEr(NO3)3·5H2O、1.299gMn(NO3)2·4H2Placing O, 3.200g of boric acid and 39.150g of citric acid in a beaker, adding distilled water, and uniformly stirring to form transparent sol;
(2) sealing the beaker, heating while stirring and refluxing for 1.5h on a constant-temperature magnetic stirrer at the temperature of 75 ℃;
(3) unsealing, continuously heating and stirring at 70 ℃ on a constant-temperature magnetic stirrer, and continuously evaporating water until transparent gel is formed;
(4) placing the beaker filled with the transparent gel into an electric heating forced air drying oven to carry out heat treatment for 2.5 hours at 180 ℃ to form fluffy precursor powder;
(5) calcining the precursor powder in a rapid heating box type resistance furnace at 750 ℃ for 3h in air atmosphere, cooling and grinding to obtain the filler (Sm)0.815Er0.015Mn0.17)BO3。
(Sm0.815Er0.015Mn0.17)BO3The preparation method of the organic silicon resin-based laser protective coating comprises the following steps:
(1) polishing the aluminum plate with 500-mesh abrasive paper for 2min, cleaning and airing;
(2) weighing 10g of high-temperature-resistant self-drying organic silicon resin and 9g of filler (Sm)0.815Er0.015Mn0.17)BO3Adding 1.33g of toluene, and stirring for 14 min;
(3) pouring the mixed coating obtained in the step (2) into a spray gun, wherein the pressure of the spray gun is 1.5MPa, the distance between a gun opening and the aluminum plate is 12cm, and uniformly spraying the mixed coating on the aluminum plate obtained in the step (1) to obtain the (Sm)0.815Er0.015Mn0.17)BO3A silicone resin coating;
(4) spraying (Sm) the spraying material in the step (3)0.815Er0.015Mn0.17)BO3Curing the aluminum plate with the organic silicon resin coating for 26 hours at room temperature to obtain the organic silicon resin-based laser protective coating.
Example 4
An organosilicon resin-based laser protective coating, the matrix of which is high-temperature resistant self-drying organosilicon resin, and the filler is (Sm)0.78Er0.02Mn0.2)BO3Mass of filler and matrixRatio 1, filler (Sm)0.78Er0.02Mn0.2)BO3The preparation method adopts a citric acid-nitrate sol-gel combustion synthesis method, and comprises the following steps:
(1) weighing 20.888gSm (NO) according to stoichiometric ratio3)3·6H2O、0.116gEr(NO3)3·5H2O、1.318gMn(NO3)2·4H2Placing O, 3.247g of boric acid and 44.135g of citric acid in a beaker, adding distilled water, and uniformly stirring to form transparent sol;
(2) sealing the beaker, heating while stirring and refluxing for 2 hours at 80 ℃ on a constant-temperature magnetic stirrer;
(3) unsealing, continuously heating and stirring at 60 ℃ on a constant-temperature magnetic stirrer, and continuously evaporating water until transparent gel is formed;
(4) placing the beaker filled with the transparent gel into an electric heating forced air drying oven to carry out heat treatment for 2 hours at the temperature of 200 ℃ to form fluffy precursor powder;
(5) calcining the precursor powder in a rapid heating box type resistance furnace at 800 ℃ for 4h in air atmosphere, cooling and grinding to obtain the filler (Sm)0.78Er0.02Mn0.2)BO3。
(Sm0.78Er0.02Mn0.2)BO3The preparation method of the organic silicon resin-based laser protective coating comprises the following steps:
(1) polishing the aluminum plate with 600-mesh abrasive paper for 2min, cleaning and airing;
(2) weighing 10g of high-temperature-resistant self-drying organic silicon resin and 10g of filler (Sm)0.78Er0.02Mn0.2)BO3Adding 1.25g of toluene, and stirring for 15 min;
(3) pouring the mixed coating obtained in the step (2) into a spray gun, wherein the pressure of the spray gun is 2MPa, the distance between a gun opening and the aluminum plate is 10cm, and uniformly spraying the mixed coating on the aluminum plate obtained in the step (1) to obtain the (Sm)0.78Er0.02Mn0.2)BO3A silicone resin coating;
(4) spraying (Sm) the spraying material in the step (3)0.78Er0.02Mn0.2)BO3Curing the aluminum plate with the organic silicon resin coating at room temperature for 30 hours to obtain the organic silicon resin-based laser protective coating.
Test example 1 temperature resistance test of laser protective coating Material
After the silicone resin-based laser protective coating provided in example 1 was subjected to heat treatment at-40 ℃, -20 ℃, 0 ℃, room temperature, 100 ℃, 200 ℃, 300 ℃ and 350 ℃, the diffuse reflection light absorption performance of the laser protective coating was analyzed by a spectrophotometer (UV 3600), and the results of the diffuse reflection absorption spectrum in the wavelength range of 900 to 1200nm are shown in fig. 1. The result of the diffuse reflection absorption spectrum of the material in the wavelength range of 1300-1650 nm is shown in figure 2. As can be seen from FIG. 1, Sm is responsible for3+Energy level transition, wherein two peak absorption bands of 900-1000 nm and 1000-1150 nm exist, and the 900-1000 nm absorption band corresponds to Sm3+Is/are as follows6H5/2→6F11/2Energy level transition and Er3+Is/are as follows4I15/2→4I11/2Energy level transition, 1000-1150 nm absorption band corresponding to Sm3+Is/are as follows6H5/2→6F9/2The energy level transition and the light reflectivity are all below 1%. FIG. 2 shows that Sm is added to the wavelength range of 1.30 to 1.65 μm3+Energy level transition, and a wide absorption band corresponding to Sm3+Energy level transition of6H5/2→6H13/2The light reflectance was 1% or less. As can also be seen from fig. 1 and 2, as the heat treatment temperature increases, the laser absorber content of the coating material increases and the reflectivity gradually decreases as the solvent volatilization increases. The influence of different high and low temperature heat treatment temperatures on the diffuse reflection light absorption performance of the laser protective coating is small, which shows that the laser protective coating material provided by the embodiment 1 has better high temperature resistance and low temperature resistance.
Test example 2 upconversion fluorescence spectroscopy test of laser protective coating material under excitation of 1.06 μm
The fluorescence spectrum test of the laser protective coating materials provided in the embodiments 1 to 4 under the excitation of 1.06 μm laser is performed by using an F4600 type fluorescence spectrometer, the test waveband range is 400 to 900nm, the test result of the embodiment 2 is taken as an example for analysis, and the test result is shown in FIG. 3.
As can be seen from FIG. 3, the laser protective coating material provided in example 2 of the present invention emits 476 and 571nm light under the excitation of laser with a wavelength of 1.06 μm, and is derived from Er3+Is/are as follows2H11/2、4S3/2→4I15/2Has up-conversion luminescence effect.
Test example 3 upconversion fluorescence spectroscopy test of laser protective coating material under excitation of 1.54 μm
The fluorescence spectrum test of the laser protective coating materials provided in the embodiments 1 to 4 under the excitation of 1.54 μm laser is performed by using an F4600 type fluorescence spectrometer, the test wavelength range is 500 to 700nm, the test result of the embodiment 2 is taken as an example for analysis, and the test result is shown in FIG. 4.
As can be seen from FIG. 4, the laser protective coating material provided in example 2 of the present invention emits red light and green light under the excitation of laser with a wavelength of 1.54 μm. Red light from Er3+Is/are as follows4F9/2→4I15/2The green light comes from Er3+Is/are as follows2H11/2、4S3/2→4I15/2Has up-conversion luminescence effect.
Test example 4 test of absorption Properties of laser protective coating Material for 10.6 μm laser
An FTIR spectrum of the filler in the laser protective coating material provided in the embodiments 1 to 4 is tested by a Nicolet5700 type Fourier transform infrared spectrometer, and the test wave number range is 3500 to 500cm-1The analysis was performed by taking the test results of example 2 as an example, and the test results are shown in fig. 5.
As can be seen from FIG. 5, the filler (Sm) in the laser protective coating material provided in example 2 of the present invention0.85Er0.01Mn0.14)BO3The infrared absorption spectrum of (1) is 1250-500 cm-1In the range of laser protectionThe protective material has a strong absorption peak to light at 944cm-1(10.6 μm wavelength), infrared absorption reached 88%, showing good optical absorption properties.
The LASER reflectivity test of the LASER protective coating materials provided in examples 1 to 4 was performed by using a LASER MODEL 10.6 μm LASER, and the test results of example 2 were analyzed, wherein the incident energy was 4.8W, the average reflection energy was 30mW, the reflectivity was 0.625%, and the LASER protective coating materials showed good optical absorption properties.
Test example 5 XRD phase analysis of fillers in laser protective coatings
Phase composition analysis of the fillers in the laser protective coatings provided in examples 1 to 4 was performed with an X-ray diffractometer (XRD, D/Max 2500), and the results are shown in fig. 6, taking the test results of example 2 as an example. As can be seen from FIG. 6, the filler (Sm)0.85Er0.01Mn0.14)BO3All the main diffraction peak positions of the three-inclined SmBO3The crystals corresponded and no other material phase peaks were present, indicating that Er and Mn entered triclinic SmBO3In the crystal structure of (1).
Test example 6 adhesion and impact resistance test of laser protective coating Material
The adhesion and impact resistance of the laser protective coating materials provided in examples 1-4 were tested according to GB/T1727-.
TABLE 1 test results of adhesion and impact resistance
As can be seen from Table 1, the materials for the laser protective coating provided in example 2 were respectively at-40 deg.C, -20 deg.C, 0 deg.C, room temperature, 100 deg.C, 200 deg.C, 300 deg.C and 35 deg.CAfter heat treatment at 0 ℃, the adhesive force is first grade, and the impact resistance is more than or equal to 50kg0.85Er0.01Mn0.14)BO3The particles are fine, the dispersibility of the filler in the matrix is good, and the laser protective coating material shows good adhesive force and impact resistance. The change of the adhesion and the impact resistance of the laser protective coating caused by different high and low temperature heat treatment temperatures is not large, which shows that the laser protective coating material provided by the embodiment 2 has better high temperature resistance and low temperature resistance.
In conclusion, the organic silicon resin-based laser protective coating provided by the invention utilizes rare earth Sm3+Is/are as follows6H5/2Ground state of the tube6F9/2Excited transition promoting filler (Sm)1-x-yErxMny)BO3In the wave band range of 1.05-1.15 μm, the infrared laser with the wavelength of 1.06 μm can be absorbed by rare earth Sm3+Is/are as follows6H5/2Ground state of the tube6H13/2Transition sum of excited states Er3+Is/are as follows4I15/2Ground state of the tube4I13/2Excited transition promoting filler (Sm)1-x-yErxMny)BO3Can absorb infrared laser with the wavelength of 1.54 mu m within the range of 1.50-1.65 mu m and utilize (Sm)1-x-yErxMny)BO3Vibration absorption of the middle B-O-B bond and [ BO3]The activated B-O in the triangular body symmetrically expands and contracts to vibrate, and can absorb 10.6 mu m infrared laser, so that the aim of laser protection is fulfilled. Er3+And Mn2+Can enter SmBO3Form (Sm) in the crystal lattice of (1)1-x-yErxMny)BO3Solid solution, Er3+The (Sm) is further enhanced by the inverse Stokes process of upconversion of 1.06 and 1.54 μm infrared laser light to visible light1-x-yErxMny)BO3Laser protection capability of (2); after Mn doping, in (Sm)1-x-yErxMny)BO3The valence change is generated in the process, so that (Sm) is doped1-x-yErxMny)BO3 The carrier concentration in the powder is increased, and the absorption of light is integratedIs improved and is further enhanced by (Sm)1-x-yErxMny)BO3The laser protection capability is achieved, and therefore the purpose of laser protection is achieved. Adopts high-temperature resistant self-drying organic silicon resin as a matrix, and is added with nano (Sm) prepared by a citric acid-nitrate sol-gel combustion synthesis method1-x-yErxMny)BO3The composite coating material prepared from the powder can bear the temperature change within the range of minus 40 ℃ to 350 ℃, the diffuse reflectance of the coating is kept below 1%, and the surface state of the coating is not changed. According to the preparation method of the laser protective coating, the laser protective coating is prepared by adopting a spraying method, the prepared coating can be cured at room temperature, and the coating has the advantages of thin thickness, uniform thickness, good surface state, high adhesive force, good flexibility, high impact strength and the like, the thickness of the coating is only 60-80 mu m, the adhesive force is more than or equal to one grade, and the impact strength is more than or equal to 50 kg.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.