Flexible bio-based glass material with adjustable optical properties and preparation method thereof

Abstract

The invention discloses a flexible bio-based glass material with adjustable optical properties and a preparation method thereof. The preparation method comprises the following steps: dissolving two different bio-based raw materials in a solvent, stirring and dissolving to form a clear solution, and completely volatilizing the solvent in the solution to obtain the flexible bio-based glass material with the phosphorescence excitation light wavelength dependence characteristic. Organic ion salt is also added into the settled solution, and the flexible bio-based glass material with phosphorescence excitation wavelength dependence and time dependence can be obtained after the solvent is completely volatilized. The bio-based glass prepared by the invention not only has high transparency and bendability, but also has high hardness, biodegradability and adjustable ultra-long room temperature phosphorescence luminescence performance. The preparation method is simple and low in cost, and shows wide application potential in the optical field.

Description

Technical Field

[0001] The present invention belongs to the technical field of flexible glass materials, and particularly relates to a flexible bio-based glass material with adjustable optical properties and a preparation method thereof. Background Art

[0002] Glass has become an indispensable material in modern society due to its excellent optical, electronic, mechanical, and thermal properties. However, the brittleness and sensitivity to deformation of glass limit its application in some fields. With the rapid development of optical display technology, wearable devices, and portable electronic devices, the market demand for flexible and ultra-thin (thickness not exceeding 0.1 mm) glass is increasing continuously. This new type of flexible glass can still maintain its structural integrity and optical properties even after being bent or twisted. This indicates that its application in fields such as display screens, semiconductors, and sensors will be revolutionary, and it is expected to make related products thinner, lighter, and more durable.

[0003] Despite the great development potential of flexible glass, its widespread application still faces many challenges. Existing production processes require high temperatures above 1000 °C, which significantly increases energy consumption. At the same time, current methods such as overflow down-draw and chemical thinning are costly. The chemical composition of flexible glass is usually limited to alkali aluminosilicates and borosilicates, which restricts the diversification and further optimization of material properties. In addition, the recycling and reuse process of flexible glass is complex, increasing the post-treatment cost and also posing challenges to environmental friendliness. Due to the difficulty of using abundant and environmentally friendly resources in the production process, the difficulty of achieving sustainable production is further increased. Therefore, in order to promote the commercialization process of flexible glass and improve its environmental friendliness, it is particularly important to solve these problems. Summary of the Invention

[0004] The purpose of the present invention is to provide a flexible bio-based glass material with adjustable optical properties and a preparation method thereof. The prepared bio-based glass not only has high transparency and bendability, but also has high hardness, biodegradability, and adjustable ultra-long room-temperature phosphorescence luminescence properties. The preparation method is simple and low-cost, demonstrating its wide application potential in the optical field.

[0005] The preparation method of the flexible bio-based glass material with adjustable optical properties is as follows: Dissolve two different bio-based raw materials in a solvent, stir to dissolve to form a clear solution, and then completely volatilize the solvent in the solution to obtain a flexible bio-based glass material with phosphorescence excitation wavelength-dependent characteristics.

[0006] One of the two different bio-based raw materials is selected from one of cellulose, konjac polysaccharide, bovine serum albumin, egg white, starch, bamboo and wood powder, lignin, animal fur; the other is selected from one of polylactic acid, silk, rice husk, sodium alginate, chitosan, gelatin, amino acid, polyamino acid.

[0007] The solvent described above is one or more of acetone, acetonitrile, ethanol, deionized water, dichloromethane, N,N-dimethylformamide, and chloroform.

[0008] The temperature at which the solvent evaporates is room temperature - 200 °C.

[0009] The evaporation time of the solvent is 1 - 10000 h.

[0010] An organic ionic salt is further added to the above-mentioned clear solution, and after the solvent has completely evaporated, a flexible bio-based glass material with both phosphorescence excitation wavelength dependence and time dependence properties is obtained.

[0011] The organic ionic salt described above is selected from one of sodium benzoate, disodium terephthalate, sodium 2-mercaptobenzimidazole, sodium N-chlorobenzenesulfonimide, ammonium p-carboxybenzeneborate, methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride, ammonium 1-pyrenecarboxylate, ammonium phenanthrene-4,5-dicarboxylate, ammonium 1,10-phenanthroline-2-carboxylate, and ammonium o-hydroxybenzoate.

[0012] The doping amount of the organic ionic salt is 0.0001% - 10% of the sum of the masses of the organic ionic salt and the two bio-based raw materials.

[0013] The present invention uses two bio-based raw materials, and by utilizing non-covalent interactions such as hydrogen bonding, electrostatic interaction, and van der Waals force between them, combined with a simple and environmentally friendly evaporation-induced self-assembly technique, a flexible glass based on natural materials is successfully prepared. In terms of material design, the dynamic hydrogen bond between the two components acts as a sacrificial bond, effectively dissipating the externally applied energy, thereby significantly improving the flexibility of the material. At the same time, the dense entanglement between these components forms a cross-linked network structure, enhancing the mechanical strength of the material and constructing a rigid molecular environment for the luminescence center, suppressing non-radiative transitions, and promoting the emission of ultra-long room temperature phosphorescence. In addition, this flexible glass can be biodegradable in soil within several months, showing good environmental friendliness. The preparation method of the present invention is simple, low-cost, and environmentally friendly, which not only gives this glass broad application prospects in the optoelectronic field but also meets the needs of modern society for green and sustainable products. Description of the Drawings

[0014] Figure 1 is the differential scanning calorimetry curve of the flexible bio-based glass material prepared in Example 1.

[0015] Figure 2 is the X-ray powder diffraction pattern of the flexible bio-based glass material prepared in Example 1.

[0016] Figure 3 is the three-point bending test curve of the flexible bio-based glass material prepared in Example 1.

[0017] Figure 4 It is a schematic diagram of the change in flexural strength of the flexible bio-based glass material prepared in Example 1 during the three-point bending cyclic test.

[0018] Figure 5 It is the phosphorescence spectrum of the flexible bio-based glass material prepared in Example 1 under ultraviolet light excitation at different wavelengths.

[0019] Figure 6 It is the phosphorescence lifetime curve of the flexible bio-based glass material prepared in Example 1 at a wavelength of 545 nm. Detailed implementation manners

[0020] Example 1 Dissolve 0.6 g of gelatin powder in 10 mL of deionized water and place it in a glass bottle. Then, put the glass bottle into an oven at 50 °C and heat it for 20 min to promote dissolution. Next, take out 2 mL of egg white from a fresh egg and add it to the dissolved gelatin solution. Stir the mixture for 5 min to ensure uniform mixing, and then pour the mixed solution into a plastic mold. Finally, place the mold containing the mixed solution at room temperature and let it evaporate naturally. After about 12 h, the solvent evaporation is basically complete, forming a flexible egg white-gelatin-based glass.

[0021] Characterize the product: (1) Conduct Fourier transform infrared spectroscopy (FTIR) tests, indicating that the main components of the flexible glass are amino acids, and there are strong hydrogen bond interactions between the amino acid molecules in the two raw materials; (2) Conduct differential scanning calorimetry (DSC) tests. The glass transition temperature of the flexible glass is 343 K, which is higher than the glass transition temperature at room temperature; (3) Conduct X-ray powder diffraction (XRD) tests. Only a very broad peak appears in the curve, indicating that the flexible glass has an amorphous structure; (4) Conduct small-angle X-ray scattering (SAXS) tests. No obvious peaks appear in the entire test range, indicating that there is a strong interaction between the two components of the glass and a molecular-level homogeneous mixing in the glass matrix; (5) Conduct scanning electron microscopy (SEM) tests. The surface of the flexible glass is smooth, and the thickness can be as low as 7.0 μm; (6) Conduct ultraviolet-visible-near-infrared transmission spectroscopy (UV-Vis-NIR) tests. The transmittance of the flexible glass is about 90% in the range of 500–1300 nm, showing high transparency; (7) Conduct three-point bending tests. The flexible glass can withstand a bending strain of about 2.0%, its flexural strength reaches 121.1 MPa, showing high flexural strength, and after 10 cyclic tests, the flexural strength remains stable; (8) Nanoindentation tests were carried out, and the hardness value of the flexible glass was 33.6 kgf·mm², indicating high hardness; (9) Delayed spectroscopy tests were carried out. As the excitation light wavelength increased, the phosphorescence color gradually changed from blue to yellowish green; indicating that the flexible glass has phosphorescent luminescence properties dependent on the excitation light wavelength, that is, room-temperature phosphorescent luminescence properties with adjustable colors.

[0022] (10) Time-resolved spectroscopy tests were carried out, indicating that the room-temperature phosphorescence lifetime of the flexible glass at a wavelength of 545 nm was 180.4 ms. Example 2

[0023] The preparation method was the same as that of Example 1, except that 1-ammonium pyrene carboxylate solution was added to the mixed solution of egg white and gelatin, thus obtaining 1-ammonium pyrene carboxylate-doped flexible bio-based glass. The specific steps were as follows: 0.04 g of 1-pyrene carboxylic acid powder and 13 μL of ammonia water (25% aqueous solution) were added to 50 mL of deionized water and stirred for 20 min to obtain a clear 1-ammonium pyrene carboxylate solution. 500 μL of this solution was taken and added to a clear solution containing 2 mL of egg white and 0.6 g of gelatin. After stirring evenly, the mixed solution was left to stand at room temperature and allowed to evaporate naturally. After a 12-hour evaporation process, 1-ammonium pyrene carboxylate-doped flexible bio-based glass materials were finally obtained.

[0024] (1) Differential scanning calorimetry tests were carried out, indicating that the glass transition temperature of the 1-ammonium pyrene carboxylate-doped flexible glass was 338 K; (2) X-ray powder diffraction tests were carried out. Only a very broad bulging peak appeared in the curve, indicating that the 1-ammonium pyrene carboxylate-doped flexible glass had an amorphous structure; (3) Three-point bending tests were carried out, indicating that the 1-ammonium pyrene carboxylate-doped flexible glass could withstand a bending strain of approximately 2.0%, its bending strength reached 114.1 MPa, and it still maintained its bending strength after 10 cycles; (4) Nanoindentation tests were carried out, indicating that the hardness value of the 1-ammonium pyrene carboxylate-doped flexible glass was 34.1 kgf·mm²; (5) Delayed spectroscopy tests were carried out, indicating that the 1-ammonium pyrene carboxylate-doped flexible glass had phosphorescent luminescence properties dependent on the excitation light wavelength, and the luminescence color gradually changed from blue to yellowish green; (6) Time-dependent delayed spectroscopy tests were carried out, indicating that the 1-ammonium pyrene carboxylate-doped flexible glass had time-dependent phosphorescent luminescence properties. As time passed, the luminescence color changed from blue, green, orange to red; (7) Time-resolved spectroscopy tests were carried out, indicating that the phosphorescence lifetime of the 1-ammonium pyrene carboxylate-doped flexible glass at a wavelength of 610 nm was as high as 104.4 ms.

Claims

1. A method for preparing a flexible bio-based glass material with adjustable optical properties, characterized in that: The specific operation of the preparation method is: dissolving two different bio-based raw materials in a solvent, stirring and dissolving to form a clear solution, and then completely volatilizing the solvent in the solution to obtain a flexible bio-based glass material with phosphorescence excitation light wavelength dependence characteristics.

2. The preparation method according to claim 1, characterized in that: The two different bio-based raw materials are one selected from cellulose, konjac polysaccharide, bovine serum albumin, egg white, starch, bamboo powder, lignin, and animal fur; and the other selected from polylactic acid, silk, rice husk, sodium alginate, chitosan, gelatin, amino acid, and polyamino acid.

3. The preparation method according to claim 1, characterized in that: The solvent is one or more of acetone, acetonitrile, ethanol, deionized water, dichloromethane, N,N-dimethylformamide and chloroform.

4. The preparation method according to claim 1, characterized in that: The solvent evaporates at a temperature between room temperature and 200°C.

5. The preparation method according to claim 1, characterized in that: The solvent volatilization time is 1-10000 h.

6. The preparation method according to any one of claims 1 to 5, characterized in that: An organic ion salt is also added to the clear solution, and a flexible bio-based glass material having both wavelength-dependent and time-dependent properties of phosphorescent excitation light is obtained after the solvent is completely evaporated.

7. The preparation method according to claim 6, characterized in that: The organic ion salt is selected from one of sodium benzoate, disodium terephthalate, sodium 2-mercaptobenzimidazole, sodium N-chlorobenzenesulfonimide, ammonium p-carboxyphenyl borate, methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride, 1-pyrenecarboxylate, phenanthrene-4,5-dicarboxylate, 1,10-phenanthroline-2-carboxylate, and ammonium o-hydroxybenzoate.

8. The preparation method according to claim 7, characterized in that: The doping amount of the organic ion salt is 0.0001%-10% of the sum of the mass of the organic ion salt and the two bio-based raw materials.

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