X-ray irradiation induced rare earth doped color-changing borate glass and preparation method thereof

Abstract

The invention relates to the technical field of rare earth glass, in particular to X-ray irradiation induced rare earth doped color-changing borate glass and a preparation method thereof.The X-ray irradiation induced rare earth doped color-changing borate glass changes color through X-ray irradiation, the color can be bleached through heating, and after the glass recovers to the initial state, the X-ray irradiation can be utilized again for coloring; the photochromic effect is utilized to effectively regulate and control rare earth ion luminescence. The catalyst comprises the following components in percentage by mole: 70-80% of B2O3; 8 to 12 percent of Bi2O3; 8%-12% of ZnO (zinc oxide); 3 to 6 percent of Na2CO3; and 0.5 to 1 percent of Eu2O3. The X-ray irradiation induced photochromic glass provided by the invention has relatively high mechanical strength and transparency, the compact network structure endows stable photochromic performance, and the application of the optical glass in the fields of information storage, X-ray detection, aviation, military and the like is expected to be widened. The process is simple, the production cost is relatively low, and the photochromic glass with high optical quality is easy to prepare and obtain.

Description

Technical Field

[0001] The invention relates to the technical field of rare earth glass, and in particular to an X-ray irradiation-induced rare earth doped color-changing borate glass and a preparation method thereof. Background Art

[0002] In the current information society, rare earths, as a strategic resource, have shown great application prospects in the fields of optics, architecture, and display. Since lanthanide elements have rich luminescence energy levels and often show excellent luminescence properties, the study of the effective regulation of the luminescence of rare earth-doped glass is of great research significance. Photochromism refers to the reversible color change of materials under light stimulation, which is a promising light storage technology. The overlap of material absorption and rare earth emission can effectively regulate the luminescence of rare earths. The bismuth borate glass system has the advantages of low melting point, high mechanical strength, high rare earth ion solubility, high transparency and high refractive index. By irradiating the glass with rays to induce color change, high light storage capacity can be achieved in photochromic glass. In addition, the irradiation source X-rays have a short wavelength (0.01-10nm) and high energy. Using rays as the information writing source is expected to break through the grating diffraction limit of traditional visible light and achieve high-precision information storage.

[0003] Therefore, the present invention prepares a new type of X-ray irradiated rare earth doped color-changing borate glass, which changes color by irradiating the glass with rays, and can fade under heating conditions. The reversible regulation of rare earth ion luminescence is achieved through the reversible photochromic effect, and the rays are further visualized to prevent ray leakage. In addition, using short-wavelength rays as information storage sources will hopefully break through the grating diffraction limit and increase information storage capacity. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing X-ray irradiation-induced rare earth doped color-changing borate glass. The X-ray irradiation-induced color-changing rare earth ion doped borate glass provided by the present invention has high mechanical strength, transparency, and refractive index, and its dense network structure gives stable color-changing performance. Through the color-changing effect of the glass, rare earth luminescence can be effectively regulated, and it is expected to broaden the application of optical glass in information storage, X-ray detection, aviation, military and other fields. In addition, the process of the present invention is simple, the production cost is low, and it is easy to prepare color-changing glass with high optical quality.

[0005] In order to achieve the above technical purpose and the above technical effect, the present invention is implemented through the following technical scheme: using X-rays to induce structural color change in the glass color, and the degree of structural color change can be used to detect whether X-ray leakage occurs. In addition, the use of a mask plate can realize the writing of optical information.

[0006] In the boron bismuth glass structure, the addition of zinc oxide introduces Zn2+ , replacing part of the boron or bismuth position, changing the network structure of the glass. Sodium carbonate decomposes to provide Na + , acting as charge-compensating ions to stabilize defects in the structure. When X-rays are irradiated, the high-energy photons excite electrons, causing them to be captured by defects and form color centers, which causes color changes. Zinc oxide may provide more defect centers, while sodium carbonate may produce a synergistic effect by adjusting the glass structure to make these defects easier to form or more stable.

[0007] An X-ray irradiation-induced rare earth doped color-changing borate glass, which changes color by X-ray irradiation, can be bleached by heating, and can be colored again by X-ray irradiation after returning to the initial state, and can regulate the luminescence of rare earth ions by photochromic effect. Its components, in terms of molar percentage, include: B2O3: 70-80%; Bi2O3: 8-12%; ZnO: 8%-12%; Na2CO3: 3-6%; Eu2O3: 0.5-1%.

[0008] On the other hand, the present invention provides a method for preparing X-ray irradiation induced color-changing rare earth ion doped borate glass, comprising the following steps:

[0009] S1: Mix B2O3, Bi2O3, ZnO, Na2CO3 and Eu2O3 in an agate mortar and grind in air for 10 minutes to make the raw materials fully mixed;

[0010] S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1050°C for 35 minutes, and then the glass liquid is poured onto a copper plate preheated to 340°C;

[0011] S3: heat treating the glass obtained in S2 in a muffle furnace at 360°C for 2 hours to remove the residual thermal stress of the glass;

[0012] S4: After grinding and polishing, the glass is irradiated with different doses of X-rays for different times;

[0013] S5: Put the discolored glass into a muffle furnace and keep it at 350℃ for 10 minutes, then the color can be erased.

[0014] Furthermore, the distribution ratio of each group in the raw material is: B2O3: 70-80%; Bi2O3: 8-12%; ZnO: 8%-12%; Na2CO3: 3-6%; Eu2O3: 0.5-1%.

[0015] On the other hand, the present invention provides the use of the above glass in X-ray irradiation-induced discoloration.

[0016] Beneficial effects of the present invention:

[0017] The present invention uses B2O3 as the main component to form a dense three-dimensional network structure, in which the cross-linking of [BO3] triangles and [BO4] tetrahedra enhances the rigidity and stability of the glass. 3+ The ions are embedded in the boron-oxygen network in the form of intermediates to form strong covalent bonds between Bi and OB, which significantly improves the polymerization degree and durability of the network. The addition of ZnO further optimizes the network structure, inhibits the formation of non-bridging oxygen, and enhances the chemical stability and mechanical strength of the glass. Experimental results show that the Vickers hardness of the glass can reach 6.5 GPa, showing excellent wear resistance and compressive resistance. During X-ray irradiation, Bi 3+ Ions can capture free electrons to form Bi 2+ The color center causes the material to have a distinct absorption band in the visible light region (500-550nm), showing a blue-green color change. By heating annealing (350℃), Bi 2+ The ability to release electrons and return to the initial state achieved up to 1,000 reversible color-changing cycles, demonstrating the potential of this material in dynamic optical applications.

[0018] Eu 3+ As a luminescence center, the probability of radiative transition of 5D0→7F2 is significantly increased. During X-ray irradiation, Bi 2+ The formation of color centers and Eu 3+ There is a competitive relationship between the luminescence processes of Eu 3+ The luminescence intensity of Bi induced by X-ray irradiation 2+ The color center is at 394nm (Eu 3+ The excitation peak of Eu 3+ The luminescence intensity decreases; this dynamic regulation based on the FRET mechanism enables the luminescence intensity and wavelength to be adjusted synchronously, which has extremely high flexibility and adjustability. In addition, combined with X-ray mask technology, high-resolution fluorescent pattern writing can be achieved in glass, further expanding the application prospects of this material in optical storage and display technology.

[0019] Eu by X-ray irradiation 3+ Ion-doped borate glass produces a color-changing effect in a short period of time, and based on the color-changing effect, it realizes the effective regulation of rare earth luminescence. This color-changing and luminescence-regulating method effectively increases the rational utilization of rare earths. Comparison of photos of different irradiation times and irradiation doses shows that high doses and long irradiation times will increase the degree of glass discoloration, showing potential application prospects in visual monitoring of X-ray doses.

[0020] By introducing Na2CO3 as a flux, the melting temperature of the glass is reduced to 1050°C, which is about 120°C lower than that of traditional borate glass, significantly reducing energy consumption. In addition, the material can be irradiated at high doses (10 4 Gy) can still maintain good optical properties and structural stability, indicating its potential for application in extreme environments. Experimental results show that after high-dose irradiation, the volume change rate of the material is less than 0.03%, and the optical uniformity remains good, making it suitable for high-radiation environments such as spacecraft windows.

[0021] The present invention utilizes the short wavelength characteristics of X-rays, and rare earth ion doped borate glass can achieve up to 1.2TB / cm 2 Data storage density. Through microbeam X-ray irradiation (20keV, beam spot 50nm), high-resolution information dot matrix can be written in glass. The storage information can be read in two ways: fluorescence mode and absorption mode. The fluorescence mode uses Eu 3+ The luminescence characteristics of the material are realized by monitoring the changes in the transmission intensity of the light, while the absorption mode is realized by monitoring the changes in the transmission intensity of the light. Experiments show that the linear response characteristics of the material in the irradiation dose range enable it to show excellent sensitivity in radiation monitoring of 0.1-100Gy, and can monitor the changes in radiation dose in real time, which has broad application prospects. It produces a significant color change effect through X-ray irradiation, and optical information can be written by using a mask. The color-changing glass can be bleached by heat treatment, which has great application prospects in the fields of reversible optical storage and military.

[0022] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0024] Figure 1 The present invention is a photograph of the glass of the present invention irradiated with X-rays at a dose of 0.00751 Gy / s for different time periods. The glass is colorless and transparent in the initial state, and the color deepens as the irradiation time increases; (a) initial state; (b) 6 min; (c) 12 min; (d) 18 min;

[0025] Figure 2These are photos of the glass of the present invention after being irradiated with different doses of X-rays for 18 minutes. It can be seen that as the dose increases, the color of the glass deepens; (a) initial state; (b) 0.00249 Gy / s; (c) 0.00557 Gy / s; (d) 0.00751 Gy / s;

[0026] Figure 3 The present invention is the transmission spectrum of the glass before and after the color change due to X-ray irradiation. The transmittance of the glass after X-ray irradiation in the 400-600nm band is significantly reduced, indicating that the color change is deepened;

[0027] Figure 4 The emission spectrum of the glass of the present invention before and after X-ray irradiation, the emission peak is concentrated around 600nm. The luminescence intensity of the glass is significantly reduced after X-ray irradiation, indicating that photochromism effectively regulates the luminescence of rare earth ions;

[0028] Figure 5 These are photos of the glass of the present invention at the initial stage, after discoloration, and after heat treatment at 350° C. for 10 minutes and bleaching. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example 1

[0031] The method for preparing X-ray irradiation-induced rare earth doped color-changing borate glass described in this embodiment includes the following steps:

[0032] S1: Weigh 15g of raw materials according to the following composition: B2O3: 73%; Bi2O3: 9%; ZnO: 11%; Na2CO3: 6%; Eu2O3: 1%; mix the raw materials in an agate mortar and grind them in air for 10 minutes to make the raw materials fully mixed;

[0033] S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1050°C for 35 minutes, and then the glass liquid is poured onto a copper plate preheated to 340°C;

[0034] S3: heat treating the glass obtained in S2 in a muffle furnace at 360°C for 2 hours to remove the residual thermal stress of the glass;

[0035] S4: grinding and polishing the glass;

[0036] S5: The glass was irradiated with X-rays for different time periods, 0 min, 6 min, 12 min, and 18 min. The X-ray dose was 0.00751 Gy / s.

[0037] In this embodiment 1, the glass is irradiated with X-rays for different time periods, such as Figure 1 As shown in (ad), the glass turns gray after X-ray irradiation. As the irradiation time of transparent colorless glass increases, the color change degree of the glass increases, showing a significant degree of color change, indicating that X-ray induced color-changing glass has excellent X-ray detection capability.

[0038] Example 2

[0039] The method for preparing a rare earth doped color-changing borate glass induced by X-ray irradiation described in this embodiment, the X-ray irradiation dose affects the degree of glass color change, and the process of photochromic regulation of rare earth ion luminescence includes the following steps:

[0040] S1: Weigh 15g of raw materials according to the following composition: B2O3: 73%; Bi2O3: 9%; ZnO: 11%; Na2CO3: 6%; Eu2O3: 1%; mix the raw materials in an agate mortar and grind them in air for 10 minutes to make the raw materials fully mixed;

[0041] S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1050°C for 35 minutes, and then the glass liquid is poured onto a copper plate preheated to 340°C;

[0042] S3: heat treating the glass obtained in S2 in a muffle furnace at 360°C for 2 hours to remove the residual thermal stress of the glass;

[0043] S4: grinding and polishing the glass;

[0044] S5: Determine the X-ray irradiation time to be 18 minutes and change different X-ray irradiation doses.

[0045] S6: The transmission spectrum and emission spectrum of the glass prepared in S4 are tested before and after discoloration by X-ray irradiation.

[0046] In this embodiment 2, the X-ray irradiation time is determined and the irradiation dose is changed, such as Figure 2 As shown in (ad), the transparent glass changes color more with the increase of irradiation dose, indicating that the glass is responsive to the X-ray irradiation dose, and further indicating that the glass prepared by the present invention can realize X-ray detection and optical information storage by using a mask. Then the transmission spectrum of the glass before and after the color change was tested, as shown in FIG. Figure 3 As shown in the figure, the transmittance of the glass decreases after the color change, indicating the excellent color change performance of the glass under X-ray irradiation. Figure 4 As shown, Eu-doped 3+ The luminescence intensity of the glass after photochromism is significantly reduced, indicating that photochromism effectively regulates the rare earth ion Eu 3+ The glow.

[0047] Example 3

[0048] The method for preparing an X-ray irradiation-induced color-changing rare earth ion-doped borate glass described in this embodiment, wherein the glass exhibits reversible X-ray irradiation color-changing properties, comprises the following steps:

[0049] S1: Weigh 15g of raw materials according to the following composition: B2O3: 73%; Bi2O3: 9%; ZnO: 11%; Na2CO3: 6%; Eu2O3: 1%; mix the raw materials in an agate mortar and grind them in air for 10 minutes to make the raw materials fully mixed;

[0050] S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1050°C for 35 minutes, and then the glass liquid is poured onto a copper plate preheated to 340°C;

[0051] S3: heat treating the glass obtained in S2 in a muffle furnace at 360°C for 2 hours to remove the residual thermal stress of the glass;

[0052] S4: grinding and polishing the glass;

[0053] S5: Determine that the X-ray irradiation time is 15 minutes, the irradiation dose is 0.00751 Gy / s, and irradiate the glass.

[0054] S6: The discolored glass is placed in a muffle furnace at 350°C, kept warm for 10 minutes, and then thermally bleached.

[0055] In this embodiment 3, the X-ray irradiation time and irradiation dose are determined, such as Figure 5 As shown in the figure, the transparent glass turns gray under X-ray irradiation, and then the color can be bleached by heat treatment, showing excellent reversible X-ray color change performance. This reversible color-changing glass promotes its application in the fields of X-ray detection, reversible information storage, and radiation protection.

[0056] The transparent X-ray irradiation-induced color-changing transparent glass obtained in Examples 1-3 of the present invention, wherein the sintering temperature is 1050°C and the time is 35 minutes, exhibits different degrees of color change under different X-ray doses and irradiation times, and the color change can be eliminated by heat treatment, showing excellent reversibility. The X-ray irradiation color-changing glass, due to its excellent X-ray response capability, shows great application prospects in the fields of information storage, X-ray dosimeters, aviation, and military.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An X-ray irradiation-induced color-changing rare earth ion-doped borate glass, characterized in that: The glass changes color by irradiating it with X-rays, and the color can be bleached by heating. After returning to its original state, it can be irradiated with X-rays again, thus utilizing the reversible photochromic effect to regulate the luminescence of rare earth ions. The components thereof, in terms of molar percentage, include: B2O3: 70-80%; Bi2O3: 8-12%; ZnO: 8%-12%; Na2CO3: 3-6%; and Eu2O3: 0.5-1%.

2. The method for preparing glass according to claim 1, characterized in that: The following steps are involved: S1: Mix B2O3, Bi2O3, ZnO, Na2CO3 and Eu2O3 in an agate mortar and grind in air for 10 minutes to make the raw materials fully mixed; S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1050°C for 35 minutes, and then the glass liquid is poured onto a copper plate preheated to 340°C; S3: heat treating the glass obtained in S2 in a muffle furnace at 360°C for 2 hours to remove the residual thermal stress of the glass; S4: After grinding and polishing, the glass is irradiated with different doses of X-rays for different times; S5: Put the discolored glass into a muffle furnace and keep it at 350℃ for 10 minutes, then the color can be erased.

3. The preparation method according to claim 2, characterized in that: The distribution ratio of each group in the raw material is: B2O3: 70-80%; Bi2O3: 8-12%; ZnO: 8%-12%; Na2CO3: 3-6%; Eu2O3: 0.5-1%.

4. Use of the glass as claimed in claim 1 in X-ray irradiation-induced discoloration.

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