Bismuthate glass coatings or films

Abstract

The invention discloses bismuthate glass. The bismuthate glass is prepared from the following main raw materials: 50 to 83 weight percent of Bi2O3, 10 to 20 weight percent of B2O3, 3 to 10 weight percent of ZnO, 3 to 10 weight percent of SiO2 and 3 to 10 weight percent of Al2O3; 0-4wt% of TiO2 is added on the basis of the total weight of the main raw materials. The invention further discloses a coating based on the bismuthate glass. The reflection performance of the glass coating is remarkably improved, the radiation refrigeration effect of the glass ceramic coating is remarkably improved, and the glass ceramic coating has the radiation protection, insulation and anti-static effects.

Description

Technical Field

[0001] This invention relates to the field of manufacturing inorganic coatings for heat and radiation protection, and more particularly to a coating for the protection of electronic devices. Background Technology

[0002] Currently, electronic devices are used in a wide range of fields. Electronic devices operating in extreme environments (such as extreme temperature fluctuations, vacuum, strong ionization, or ultraviolet radiation) require special coating materials for protection to prevent failure. Glass-ceramic inorganic coatings have become a popular protective material for electronic devices in extreme environments due to their low-cost manufacturing and long-term environmental stability. However, current glass-ceramic coatings used for protection are typically quite thick, exceeding 350 micrometers (XP Zhao, TY Li, H. Xie, H. Liu, LZ Wang, Asolution-processed radiative cooling glass, Science 2023, 382, ​​684.), which limits their application in aerospace electronics.

[0003] How to significantly improve the thermal protection performance of glass-ceramic coatings while significantly reducing the thickness of the coating material (i.e., making it as thin as possible) has always been a long-term challenge for aerospace protective materials technology.

[0004] The above content is only used to help understand the technical solution of the present invention and does not represent an admission that the above content is prior art. Summary of the Invention

[0005] The purpose of this invention is to provide an inorganic protective coating for electronic devices that significantly reduces the thickness while still possessing excellent UV blocking, thermal protection, and radiation resistance properties.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows: Bismuthate glass is prepared from the following main raw materials: Bi₂O₃ 50-83wt%, B₂O₃ 10-20wt%, ZnO 3-10wt%, SiO₂ 3-10wt%, Al₂O₃ 3-10wt%; and 0-4wt% TiO₂ is added based on the total weight of the main raw materials.

[0007] Preferably, the main raw material ratio is: Bi2O3 80wt%, B2O3 11wt%, ZnO 3wt%, SiO2 3wt%, Al2O3 3wt%.

[0008] The bismuthate glass was prepared by melt water quenching.

[0009] The preferred method of the melt-quenching method is to melt the raw material at 1200 °C for 20 minutes and then pour it into deionized water to obtain the bismuthate glass.

[0010] A bismuthate glass coating or film, wherein the raw materials for preparing the coating or film include bismuthate glass, and the addition ratio of ink oil is 15-18 wt% and the addition ratio of dispersant is 0.5-1.0 wt% based on the weight of bismuthate glass.

[0011] The method for preparing the bismuthate glass coating or thin film includes the following steps: S1. Grind bismuthate glass into powder; S2. Bismuthate glass powder, ink oil, and dispersant are mixed to prepare a slurry, and then the slurry is applied to a substrate to form a coating or film; S3. Heat-treat the coating or film, then cool it to room temperature; The heat treatment refers to holding the temperature at 560-700 ℃.

[0012] A bismuthate glass-ceramic coating or film, wherein the raw materials for preparing the coating or film include 50-60 wt% bismuthate glass and 40-50 wt% ceramic powder, and based on the total weight of bismuthate glass and ceramic powder, the addition ratio of ink is 18-20 wt%, and the addition ratio of dispersant is 0.5-1.0 wt%; the ceramic powder is preferably TiO2 or ZnO.

[0013] The method for preparing the bismuthate glass-ceramic coating or thin film includes the following steps: S1. Thoroughly grind bismuthate glass and ceramic powder to obtain a mixed powder; S2. Mix the powder, ink oil, and dispersant to prepare a slurry, and then apply the slurry to a substrate to form a coating or film; S3. Heat-treat the coating or film, then cool it to room temperature.

[0014] The heat treatment refers to holding the temperature at 560-700 ℃.

[0015] By adopting the above technical solution, the present invention has the following beneficial technical effects: 1. This invention, through glass composition control and combined with heat treatment process, allows for adjustment of the type and content of crystals as needed.

[0016] 2. Embodiment 2 of the present invention consists of a continuous glass phase, with snowflakes or cubic crystals on the coating surface, and contains spherical glass phases embedded in the glass coating matrix. The reflectivity of the coating is significantly improved, thereby providing better thermal protection.

[0017] 3. Embodiment 3 of the present invention consists of a continuous glass phase, ceramic, and crystals precipitated from the glass phase. The raw materials include bismuthate glass. Under the same conditions, the radiation cooling performance of the glass-ceramic coating is significantly improved.

[0018] 4. The device combining the bismuthate glass ceramic coating and the ultrathin flexible glass substrate of the present invention has good flexibility and meets the application scenarios that require flexibility.

[0019] 5. The preparation methods of the bismuthate glass coating and the bismuthate-containing glass ceramic coating of the present invention are suitable for mass production, have low production costs, and can be made into coatings or films as needed.

[0020] 6. The bismuthate-containing glass-ceramic coating of the present invention has radiation protection, insulation and antistatic effects. Attached Figure Description

[0021] Figure 1 and Figure 2 The image shows the surface microstructure of the Ti-3 bismuthate glass coating in Example 2. Figure 3 This is a cross-sectional microscopic image of the Ti-3 bismuthate glass coating from Example 2; Figures 4A-4I The X-ray diffraction pattern of the bismuthate glass coating in Example 2 is shown below. Figure 5 The X-ray diffraction pattern of the Ti-4 bismuthate glass coating in Example 2 is shown below. Figure 6 The data are transmission electron microscopy test data of the Ti-3 bismuthate glass coating in Example 2; Figure 7 The data are from atomic force microscopy of the Ti-3 bismuthate glass coating in Example 2. Figure 8 Photographs and reflectance spectra of the bismuthate glass coating in Example 2; Figure 9 The elastic modulus and hardness data of the bismuthate glass coating in Example 2 are as follows; Figure 10 The dielectric constant data for the bismuthate glass coating in Example 2 are shown. Figure 11 A photograph of the Ti-3-ZN40 bismuthate glass-ceramic coating from Example 3; Figure 12 The image shows the surface microstructure of the bismuthate glass-ceramic coating in Example 3. Figure 13 This is a cross-sectional microstructure image of the bismuthate glass-ceramic coating of Example 3; Figure 14 Photographs and reflectance spectra of the bismuthate glass-ceramic coating of Example 3; Figure 15 The reflectance spectra of the Ti-3-40 bismuthate glass-ceramic coating in Example 3 at different thicknesses are shown. Figure 16 Example 3: Bending strength test of Ti-3-40 bismuthate glass-ceramic coating; Figure 17 Adhesion test of Ti-3-40 bismuthate glass-ceramic coating in Example 3; Figure 18 The data are from atomic force microscopy of the Ti-3-40 bismuthate glass-ceramic coating in Example 3. Figure 19 The data are from atomic force microscopy of the Ti-3-50 bismuthate glass-ceramic coating in Example 3. Figure 20 Infrared emissivity of the Ti-3-40 bismuthate glass-ceramic coating in Example 3; Figure 21 The data show the radiation resistance of the Ti-3-40 bismuthate glass-ceramic coating in Example 3. Detailed Implementation

[0022] It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention.

[0023] Example 1: A bismuthate glass, prepared from the following main raw materials: Bi₂O₃ 50-83wt%, B₂O₃ 10-20wt%, ZnO 3-10wt%, SiO₂ 3-10wt%, Al₂O₃ 3-10wt%. Based on the total weight of the main raw materials, 0-4wt% TiO₂ is additionally added to the bismuthate glass.

[0024] Preferably, the main raw material ratio is: Bi2O3 80wt%, B2O3 11wt%, ZnO 3wt%, SiO2 3wt%, Al2O3 3wt%.

[0025] The bismuthate glass was prepared by melt water quenching.

[0026] The preferred method of the melt-quenching method is to melt the raw material at 1200 °C for 20 minutes and then pour it into deionized water to obtain the bismuthate glass.

[0027] This invention prepared bismuthate glasses with five components. The main raw materials were: 80wt% Bi2O3, 11wt% B2O3, 3wt% ZnO, 3wt% SiO2, and 3wt% Al2O3. 0wt%, 1wt%, 2wt%, 3wt%, and 4wt% TiO2 were added respectively, and the resulting bismuthate glasses were named Ti-0, Ti-1, Ti-2, Ti-3, and Ti-4, respectively.

[0028] Example 2: The bismuthate glass can be used to prepare bismuthate glass coatings or films. The raw materials for preparing the coatings or films include bismuthate glass, and the addition ratio of ink oil is 15-18 wt% and the addition ratio of dispersant is 0.5-1.0 wt%, based on the weight of bismuthate glass.

[0029] The method for preparing the coating or thin film includes the following steps: S1. Grind bismuthate glass into powder; S2. Bismuthate glass powder, ink oil, and dispersant are mixed to prepare a slurry. The slurry is then processed by conventional processes such as printing, coating, and spin coating to form a coating or film on a carrier. The carrier can be a glass substrate or other substrate. S3. Heat-treat the coating or film, then cool it to room temperature.

[0030] The heat treatment refers to holding the temperature at 560-700 ℃.

[0031] Preferably, the heat treatment temperature is 650℃ and 675℃.

[0032] The heat preservation time is generally 7-10 minutes, which can be adjusted to shorten or extend the time according to the actual situation, so as to meet the required time for the formation of the crystal phase.

[0033] This invention utilizes the five bismuthate glasses from Example 1 and prepares bismuthate glass coatings under different heat treatment conditions according to the method of this example.

[0034] The proportions of the raw materials used in the preparation of the glass coating are shown in Table 1: Table 1

[0035] The microstructure of the Ti-3 bismuthate glass coating (heat-treated at 650 °C for 10 minutes) was characterized, revealing snowflake-like patterns on the surface. Figure 1 ) and granular ( Figure 2 The structure contains dispersed spherical glass phases. Figure 3 The spherical dispersed phase was characterized as a silicon-rich phase.

[0036] The energy dispersive spectroscopy (EDS) data of the surface snowflake crystals are shown in Table 2 below. The calculated mass ratio of Si to Bi is 0.0939, which is very close to the theoretical ratio of these elements in Bi₄(SiO₄)₃ crystal (0.101), indirectly verifying the composition of the snowflake crystals.

[0037] Table 2

[0038] Energy dispersive spectral data of dispersed spherical glass phases ( Figure 3 The marked test areas are shown in Table 3 below: Table 3

[0039] X-ray diffraction patterns of coatings heat-treated at different temperatures are shown below. Figure 4A-4I As shown (unless otherwise noted, the heat treatment time is 10 minutes), Figure 4B The Ti-0 sample was heat-treated at 700 °C for 30 minutes. The crystals precipitated from the coating were characterized as Bi2Ti2O7 (crystal number PDF# 32-0118) and Bi4(SiO4)3 (crystal number PDF# 35-1007). Figure 5 This is the X-ray diffraction pattern of the Ti-4 bismuthate glass coating sample after heat treatment at 625℃ for 7 minutes. The experimental data show (Figure 4 and...) Figure 5 Different crystal contents and types in the final coating can be obtained by adjusting the amount of TiO2 added to the bismuthate glass coating component and the coating heat treatment temperature.

[0040] The bismuthate glass coating (Ti-3 bismuthate glass coating, heat-treated at 650℃ for 10 minutes) was ground into powder and subjected to transmission characterization. Figure 6 A), energy spectrum data ( Figure 6 B) indicates that the elements precipitated from the Ti-3 bismuthate glass coating include Bi, O, Si, and Ti, and that in the crystal regions containing Bi, Ti, and O elements ( Figure 6 Within the marked region (A), two distinct crystal planes were identified, with interplanar spacings of 0.234 nm and 0.297 nm, respectively. Figure 6 C). By comparing the lattice parameters of Bi2Ti2O7 crystals, corresponding to the (662) and (444) crystal planes respectively, the electron diffraction pattern of the (662) crystal plane was obtained by Fourier transform. Figure 6 D) The data are consistent with those provided in existing literature. Transmission electron microscopy further confirmed the structure of the precipitated crystals. The surface roughness of the coating (Ti-3) was also characterized using atomic force microscopy. Figure 7 ).

[0041] Photographs and reflectance spectra of the coating, such as Figure 8 As shown, the reflectivity of the coatings under different heat treatment regimes was tested. For products treated at 650 °C, the reflectivity of the Ti-3 bismuthate glass coating and the Ti-4 bismuthate glass coating did not differ significantly.

[0042] The nanoindentation test results of the coating (heat treated at 580 ℃ for 10 minutes) show that ( Figure 9 The elastic modulus and hardness of the coating increase with the addition of TiO2.

[0043] The dielectric constant of the coating is as follows Figure 10 As shown, the dielectric constant of the Ti-4 sample increases significantly when prepared at 650 °C.

[0044] Example 3: The present invention also provides another bismuthate glass ceramic coating or film, wherein the raw materials for preparing the coating or film include 50-60 wt% bismuthate glass and 40-50 wt% ceramic powder, and the addition ratio of ink oil is 18-20 wt% and the addition ratio of dispersant is 0.5-1.0 wt% based on the total weight of bismuthate glass and ceramic powder.

[0045] The ceramic powder is preferably TiO2 or ZnO.

[0046] The method for preparing the coating or thin film includes the following steps: S1. Thoroughly grind bismuthate glass and ceramic powder to obtain a mixed powder; S2. A slurry is prepared by mixing powder, ink oil, and dispersant, and then the slurry is applied to a substrate as a coating or film using conventional processes such as printing, coating, or spin coating. The substrate may be a glass substrate or other substrate. S3. Heat-treat the coating or film, then cool it to room temperature.

[0047] The heat treatment refers to holding the temperature at 560-700 ℃.

[0048] Preferably, the heat treatment temperature is 650 °C.

[0049] This invention utilizes Ti-0 bismuthate glass and Ti-3 bismuthate glass, respectively, and adds ceramic powder. According to the method of this embodiment, two coatings were prepared under heat treatment at 650 ℃ (the raw material ratio is: 60 wt% bismuthate glass, 40 wt% TiO2 ceramic powder, 18 wt% ink oil and 0.5 wt% dispersant based on the total weight of bismuthate glass and ceramic powder), and named Ti-0-40 and Ti-3-40, respectively.

[0050] Ceramic powder can be replaced with ZnO. A ZnO bismuthate glass-ceramic coating was prepared under heat treatment at 650 ℃ (the raw material ratio was: 60wt% Ti-3 bismuthate glass, 40wt% ZnO, 19wt% ink oil, and 0.5wt% dispersant based on the total weight of Ti-3 bismuthate glass and ZnO), named Ti-3-ZN40. A photo of the product Ti-3-ZN40 is shown below. Figure 11 As shown.

[0051] Figure 12 The surface microstructure of the bismuthate glass-ceramic coating. Figure 12 A is a microscopic image of the Ti-0-40 coating. Figure 12 B and 12C are microscopic images of different regions of the Ti-3-40 coating. Compared with the Ti-0-40 coating, the Ti-3-40 coating surface has snowflake-like crystals and bulk granular crystals, which precipitate from the bismuthate glass matrix.

[0052] The cross-sectional microstructure of bismuthate glass-ceramic coatings is as follows Figure 13 As shown (the area marked by the white line in the figure is the coating, and the bottom is the glass substrate), the thickness of the Ti-3-40 coating is approximately 40.5 μm.

[0053] The reflectance spectrum of the coating is as follows Figure 14 As shown, the reflectivity of the Ti-3-40 coating is significantly improved compared to the Ti-0-40 coating. Furthermore, thickness affects the reflectivity of the coating; the reflectivity spectra of the Ti-3-40 coating at different thicknesses are shown below. Figure 15 As shown.

[0054] The flexural strength test of the Ti-3-40 coating is as follows: Figure 16 As shown, it has a strength of 391.5 MPa and can withstand a bending angle of 65 degrees.

[0055] Adhesion test of Ti-3-40 coating as follows Figure 17 As shown, the results indicate that after the scratch test, the area of ​​coating peeling off is less than 5%, and the adhesion level of the sample test reaches level 1 (GB / T9286-2021 / ISO2409: 2020).

[0056] The surface roughness of the Ti-3-40 and Ti-3-50 coatings (prepared using the following raw material ratios: 50 wt% Ti-3 bismuthate glass, 50 wt% TiO2 ceramic powder, 20 wt% ink, 1.0 wt% dispersant, and heat-treated at 650 ℃) was characterized using atomic force microscopy. The test results are as follows: Figure 18 (Ti-3-40 coating) and Figure 19 (Ti-3-50 coating).

[0057] The radiative cooling performance of the coating is also related to its infrared emissivity, such as... Figure 20 As shown, the average emissivity of the sample is 0.88 in the 7-15 μm wavelength range. The Ti-3-40 coating was subjected to vacuum ultraviolet irradiation (irradiation power 600 W / m). 2 Vacuum degree ≤7*10 -3 After 4 weeks (i.e., 28 days), the reflectance did not change significantly. Figure 21 A). The Ti-3-40 coating was subjected to gamma irradiation (total irradiation dose 5*10).5 After Gy), the reflectivity did not change significantly. Figure 21 B).

[0058] Reflectance test instructions: Using analytical grade BaSO4 as the standard (powder tablet), the reflectance of the coated sample in the wavelength range of 250-2000 nm was tested at room temperature using an ultraviolet-visible-near-infrared spectrometer (instrument model UV3600, Japan) with the integrating sphere method.

[0059] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification, or direct or indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A bismuthate glass characterized in that, The raw material for preparation comprises a main raw material including the following components: Bi2O3 50-83 wt%, B2O3 10-20 wt%, ZnO 3-10 wt%, SiO2 3-10 wt%, Al2O3 3-10 wt%; 0-4 wt% of TiO2 is added based on the total weight of the main raw material.

2. The bismuthate glass of claim 1, wherein, The main raw material is proportioned as follows: Bi2O3 80 wt%, B2O3 11 wt%, ZnO 3 wt%, SiO2 3 wt%, Al2O3 3 wt%.

3. The bismuthate glass of claim 1, wherein, The bismuthate glass is prepared by a melt water quenching method.

4. The bismuthate glass according to claim 3, wherein, The melt water quenching method is that the raw material is melted at 1200 ℃ for 20 minutes, and then poured into deionized water to obtain the bismuthate glass.

5. A bismuthate glass coating or film, characterized in that, The raw material for preparation comprises the bismuthate glass according to claim 1, and the adding proportion of the ink oil is 15-18 wt% and the adding proportion of the dispersant is 0.5-1.0 wt% based on the weight of the bismuthate glass. The preparation method comprises the following steps: S1. grinding the bismuthate glass into powder; S2. mixing the bismuthate glass powder, the ink oil and the dispersant to prepare a slurry, and then preparing a coating or a film on a substrate from the slurry; S3. heat treating the coating or the film, and then cooling to room temperature; The heat treatment refers to heat preservation at 560-700 ℃.

6. A bismuthate glass-ceramic coating or film, characterized in that, The raw material for preparation comprises the bismuthate glass according to claim 1 50-60 wt% and ceramic powder 40-50 wt%, and the adding proportion of the ink oil is 18-20 wt% and the adding proportion of the dispersant is 0.5-1.0 wt% based on the total weight of the bismuthate glass and the ceramic powder. The preparation method comprises the following steps: S1. grinding the bismuthate glass and the ceramic powder to obtain a mixed powder; S2. mixing the mixed powder, the ink oil and the dispersant to prepare a slurry, and then preparing a coating or a film on a substrate from the slurry; S3. heat treating the coating or the film, and then cooling to room temperature. The heat treatment refers to heat preservation at 560-700 ℃.

7. The bismuthate glass ceramic coating or film of claim 6, wherein, The ceramic powder is TiO2 or ZnO.

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