X-ray excited borate long persistent phosphor and method of making same

Abstract

The application provides an X-ray excited borate long afterglow luminescent material and a preparation method thereof, relates to the field of inorganic functional materials, and the chemical composition expression of the borate long afterglow material is M3(BO3)2:N, wherein M=Ca, Sr; N=Bi, Pr, Ce. The long afterglow luminescent material can be effectively excited by X-ray, has slow afterglow decay, strong initial afterglow intensity and long afterglow duration. The preparation method has the characteristics of simple preparation process, easy operation, low equipment requirement and no environmental pollution in the preparation process. The borate long afterglow luminescent material has potential application value in the fields of photodynamic therapy, photocatalysis, disinfection and sterilization, optical storage and anti-counterfeiting.

Description

Technical Field

[0001] This invention belongs to the field of inorganic functional materials technology, and in particular relates to an X-ray excited borate long afterglow luminescent material and its preparation method. Background Technology

[0002] Long-afterglow materials are photoluminescent materials that emit visible light when excited by a light source, storing some of the acquired light energy. After excitation stops, they slowly release the energy in the form of light and can continue to emit light for several hours. Benefiting from not requiring real-time excitation, the application fields of long-afterglow materials have expanded from traditional emergency signs and luminous toys to high-energy ray detection, anti-counterfeiting encryption of information, fluorescent coatings, fluorescent probes, and medical diagnosis. Currently, research on long-afterglow materials in the visible light region is relatively mature, especially those in the blue and green light regions, which have been widely used in nighttime traffic signs, fire emergency signs, and arts and crafts.

[0003] Currently, the most common green and blue long-afterglow materials are still rare-earth activated aluminates and silicates, such as SrAl2O4:Eu 2+ ,Dy 3+ ,CaAl2O4:Eu 2+ ,Dy 3+ and Sr2MgSi2O7:Eu 2+ ,Dy 3+ These fluorescent materials are all common emergency marking materials. Borate phosphors, as an important branch of rare-earth long-afterglow materials, have many advantages. Compared to luminescent materials based on silicates, aluminates, and phosphates, borate phosphors have lower synthesis temperatures, simpler processes, more stable chemical properties, better color rendering in lamps, higher luminous efficiency, and lower light decay. They also have a cost advantage over luminescent materials based on rare-earth oxides, making them a valuable foundation for research on luminescent materials such as ultraviolet excitation, X-ray excitation, field emission, electroluminescence, and thermoluminescence.

[0004] Because applications such as those involving human tissue and catalytic environments (e.g., aqueous media) require excitation sources with strong penetrating power, low-power X-rays are widely used as excitation sources for afterglow luminescence materials due to their extremely strong penetrating power and low radiation damage. However, high-efficiency X-ray-excited borate long afterglow materials have rarely been reported, which to some extent limits the application potential of borate long afterglow materials in fields such as information anti-counterfeiting and bioimaging.

[0005] Therefore, developing a series of high-performance X-ray excited borate long afterglow materials is of great research significance and application value. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention proposes an X-ray excited borate long afterglow luminescent material and its preparation method.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] An X-ray excited borate long afterglow luminescent material has the chemical composition formula: M3(BO3)2:N, where M = Ca or Sr; N = Bi, Pr or Ce.

[0009] Furthermore, in the raw materials of the X-ray excited borate long afterglow luminescent material: the compound containing M is a carbonate of M, the compound containing B is boric acid, and the compound containing N is an oxide of N.

[0010] Furthermore, the M-containing compound is CaCO3 or SrCO3, and the N-containing compound is Bi2O3 or Pr6O. 11 Or CeO2.

[0011] Furthermore, the purity of the M-containing compound, the B-containing compound, and the N-containing compound was all 99.99%.

[0012] The borate long-afterglow luminescent material of the present invention can be excited by X-rays. After the excitation source is removed, the material has a strong afterglow intensity, a slow afterglow decay, and a long afterglow duration. It is expected to generate a great impetus in the research and application of afterglow materials, such as using this material in fields such as security display, instrument display, photodynamic therapy, photocatalysis, sterilization and disinfection, or information encryption.

[0013] A method for preparing the X-ray excited borate long afterglow luminescent material includes the following steps:

[0014] Weigh out the compounds containing M, B, and N according to the stoichiometric ratio of M3(BO3)2:N, mix them, add anhydrous ethanol, and grind them to obtain a uniformly ground mixed powder.

[0015] The mixed powder is pre-calcined in air at 500-800°C for 2-6 hours to obtain a pre-calcined product, preferably pre-calcined at 800°C for 2 hours;

[0016] The pre-calcined product is heated to 1000-1300℃ in a reducing atmosphere or air atmosphere and calcined for 4-10 hours. It is then naturally cooled to room temperature in the furnace to obtain X-ray excited borate long afterglow luminescent material. Preferably, the temperature is raised to 1250℃ and calcined for 4 hours.

[0017] Furthermore, in the preparation method of the X-ray excited borate long afterglow luminescent material, the heating rate during pre-calcination is 3-5℃ / min to avoid impurities caused by borate precipitation due to excessively rapid temperature rise.

[0018] Furthermore, in the method for preparing the X-ray excited borate long afterglow luminescent material, the heating rate during calcination is 3-5℃ / min. This avoids the precipitation of borate and the generation of impurities due to excessively rapid temperature increases.

[0019] Furthermore, before pre-calcination, the uniformly ground mixed powder is dried in an oven at 80-100℃ to remove as much ethanol as possible from the sample, so as to avoid the generation of carbon impurities during the calcination process, which would reduce the afterglow luminescence of the sample.

[0020] Furthermore, the preparation method of the X-ray excited borate long afterglow luminescent material is as follows:

[0021] Mixing and grinding: Weigh out compounds containing M, B, and N according to the stoichiometric ratio of M3(BO3)2:N and mix them. Add anhydrous ethanol to the mixed material and grind it in an agate mortar for 40 minutes to obtain a uniformly ground powder. Dry the uniformly ground powder in an oven at 80-100℃.

[0022] Pre-calcination: The dried mixed powder is placed in an alumina crucible and heated to 800°C at a heating rate of 5°C / min in an air atmosphere (i.e., atmospheric environment) for 2 hours to obtain the pre-calcined product.

[0023] High-temperature sintering: After the pre-calcined product is taken out and ground, it is placed in an alumina crucible and heated to 1250°C in a reducing atmosphere or air atmosphere. It is calcined for 4 hours and then naturally cooled to room temperature with the furnace to obtain X-ray excited borate long afterglow luminescent material.

[0024] The method for testing the luminescence performance of X-ray excited borate long-afterglow luminescent materials is as follows: grind the X-ray excited borate long-afterglow luminescent material, put it into a transparent test tube, and test its luminescence performance after X-ray excitation.

[0025] This invention employs a high-temperature solid-state synthesis method to prepare X-ray excited borate long afterglow luminescent materials, using M carbonate, boric acid, and N oxide as raw materials. The method is inexpensive and environmentally friendly, with a simple and easy-to-operate preparation process, low equipment requirements, and no environmental pollution during the preparation process.

[0026] Because boric acid is highly volatile, this invention adds an excess (up to 15%) of boric acid during the preparation process to ensure complete synthesis of the product, thereby improving the purity and luminescence properties of the prepared material. Unlike existing preparation methods, this invention involves calcination in an air atmosphere. The calcination atmosphere is determined based on the dopant ions (luminescent centers) of the target product. If the dopant ions are easily oxidized, and the luminescence intensity is significantly reduced after oxidation, calcination in a reducing atmosphere is necessary.

[0027] The application of the X-ray excited borate long afterglow luminescent material in the field of photodynamic therapy.

[0028] The application of the X-ray excited borate long afterglow luminescent material in the field of information encryption.

[0029] The application of the X-ray excited borate long afterglow luminescent material in the field of photocatalysis.

[0030] The application of the X-ray excited borate long afterglow luminescent material in the field of sterilization and disinfection.

[0031] The application of the X-ray excited borate long afterglow luminescent material in the fields of security display or instrument display.

[0032] Compared with the prior art, the present invention has the following advantages and technical effects:

[0033] (1) The present invention uses a high-temperature solid-state method to prepare borate long afterglow luminescent materials. The preparation process is simple, easy to operate, requires low equipment, and does not pollute the environment.

[0034] (2) The borate long-afterglow luminescent material of the present invention can be effectively excited by X-rays to produce long-afterglow luminescence with high afterglow intensity, long duration, and slow decay. Experimental results show that the borate long-afterglow luminescent material prepared by the present invention can produce afterglow in the range of 300nm-400nm after excitation, and the main peaks of the afterglow spectrum are located near 353nm (Pr), 365nm (Ce), and 396nm (Bi).

[0035] (3) The borate long afterglow luminescent material prepared by the present invention can be mixed with organic polymer materials such as epoxy resin and curing agent to form a thin film or resin body, which can be used as a luminescent thin film or a blue afterglow luminescent device, laying a solid foundation for its practical application in emergency indicator devices, optoelectronic devices, imaging display devices and bioimaging fields. Attached Figure Description

[0036] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0037] Figure 1 The X-ray diffraction patterns of the borate long afterglow luminescent materials prepared in Examples 1-3 of this invention are shown below.

[0038] Figure 2 The Bi-doped borate long afterglow luminescent material Ca3(BO3)2:Bi prepared in Example 1 of this invention 3+ Excitation and emission spectra;

[0039] Figure 3 The Bi-doped borate long afterglow luminescent material Ca3(BO3)2:Bi prepared in Example 1 of this invention 3+ Afterglow spectrum after X-ray excitation for 1 minute;

[0040] Figure 4 The Bi-doped borate long afterglow luminescent material Ca3(BO3)2:Bi prepared in Example 1 of this invention 3+ The afterglow decay curve after 1 minute of X-ray excitation, with a test time of 5400 seconds;

[0041] Figure 5 The Pr-doped borate long afterglow luminescent material Ca3(BO3)2:Pr prepared in Example 2 of this invention 3+ Excitation and emission spectra;

[0042] Figure 6 The Pr-doped borate long afterglow luminescent material Ca3(BO3)2:Pr prepared in Example 2 of this invention 3+ Afterglow spectrum after X-ray excitation for 1 minute;

[0043] Figure 7 The Pr-doped borate long afterglow luminescent material Ca3(BO3)2:Pr prepared in Example 2 of this invention 3+ The afterglow decay curve after 1 minute of X-ray excitation, with a test time of 5400 seconds.

[0044] Figure 8 The Ce-doped borate long afterglow luminescent material Ca3(BO3)2:Ce prepared in Example 3 of this invention 4+ Excitation and emission spectra;

[0045] Figure 9 The Ce-doped borate long afterglow luminescent material Ca3(BO3)2:Ce prepared in Example 3 of this invention 4+ Afterglow spectrum after X-ray excitation for 1 minute;

[0046] Figure 10 The Ce-doped borate long afterglow luminescent material Ca3(BO3)2:Ce prepared in Example 3 of this invention 4+ The afterglow decay curve after 1 minute of X-ray excitation, with a test time of 5400 seconds.

[0047] Figure 11 The X-ray diffraction patterns of the borate long afterglow luminescent materials prepared in Examples 4-6 of this invention are shown below.

[0048] Figure 12 The Bi-doped borate long afterglow luminescent material Sr3(BO3)2:Bi prepared in Example 4 of this invention3+ Excitation and emission spectra;

[0049] Figure 13 The Bi-doped borate long afterglow luminescent material Sr3(BO3)2:Bi prepared in Example 4 of this invention 3+ Afterglow spectrum after X-ray excitation for 1 minute;

[0050] Figure 14 The Pr-doped borate long afterglow luminescent material Sr3(BO3)2:Pr prepared in Example 5 of this invention 3+ Excitation and emission spectra;

[0051] Figure 15 The Pr-doped borate long afterglow luminescent material Sr3(BO3)2:Pr prepared in Example 5 of this invention 3+ Afterglow spectrum after X-ray excitation for 1 minute;

[0052] Figure 16 The Ce-doped borate long afterglow luminescent material Sr3(BO3)2:Ce prepared in Example 6 of this invention 4+ Excitation and emission spectra;

[0053] Figure 17 The Ce-doped borate long afterglow luminescent material Sr3(BO3)2:Ce prepared in Example 6 of this invention 4+ Afterglow spectrum after X-ray excitation for 1 minute;

[0054] Figure 18 The Ce-doped borate long afterglow luminescent material Sr3(BO3)2:Ce prepared in Example 6 of this invention 4+ The afterglow decay curve after 1 minute of X-ray excitation, with a test time of 5400 seconds. Detailed Implementation

[0055] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0056] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0057] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0058] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0059] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0060] Unless otherwise specified, the room temperature in the embodiments of the present invention is 25±2℃.

[0061] All raw materials used in the embodiments of this invention were obtained through commercial purchase. The raw materials involved in the embodiments include CaCO3, SrCO3, Bi2O3, and Pr6O. 11 The purity of CeO2 and boric acid is 99.99%.

[0062] The technical solution of the present invention will be further illustrated by the following embodiments.

[0063] Example 1

[0064] 1.1999 g CaCO3, 0.0028 g Bi2O3, and 0.5441 g H3BO3 were weighed separately. The mixture was placed in an agate mortar, and anhydrous ethanol was added at room temperature. The mixture was then ground for 40 min, followed by drying in a 90°C oven to obtain a mixed powder. The powder was placed in an alumina crucible and heated to 800°C at a rate of 5°C / min under atmospheric conditions for 2 hours to obtain a pre-calcined sample. The pre-calcined sample was then removed, ground, and placed in an alumina crucible. The temperature was increased to 1250°C at a rate of 5°C / min for 4 hours, followed by natural cooling to room temperature to obtain a sample with the composition Ca3(BO3)2:Bi. 3+ The long-afterglow luminescent sample material was ground and then placed in a transparent test tube to test its luminescence properties.

[0065] Example 2

[0066] Weigh out 1.1999g of CaCO3 and 0.0020g of Pr6O, respectively. 11 Mix the above raw materials with 0.5441g H3BO3 and place them in an agate mortar. Add anhydrous ethanol at room temperature and grind for 40 minutes. Then dry in a 90℃ oven to obtain a mixed powder. Place the mixed powder in an alumina crucible and heat it to 500℃ at a rate of 3℃ / min under atmospheric conditions for 6 hours to obtain a pre-calcined sample. Remove the pre-calcined sample, grind it, and place it in an alumina crucible. Heat it to 1000℃ at a rate of 3℃ / min for 10 hours, and then cool it naturally to room temperature to obtain the sample with the composition Ca3(BO3)2:Pr. 3+ The long-afterglow luminescent sample material was ground and then placed in a transparent test tube to test its luminescence properties.

[0067] Example 3

[0068] Weigh out 1.1971g CaCO3, 0.0068g CeO2, and 0.5688g H3BO3 respectively. Mix the raw materials and place them in an agate mortar. Add anhydrous ethanol at room temperature and grind for 40 minutes. Then dry in a 90℃ oven to obtain a mixed powder. Place the mixed powder in an alumina crucible and heat it to 800℃ at a rate of 5℃ / min under atmospheric conditions for 2 hours to obtain a pre-calcined sample. Remove the pre-calcined sample, grind it, and place it in an alumina crucible. Heat it to 1250℃ at a rate of 5℃ / min for 4 hours, and then cool it naturally to room temperature to obtain the sample with the composition Ca3(BO3)2:Ce. 4+ The long-afterglow luminescent sample material was ground and then placed in a transparent test tube to test its luminescence properties.

[0069] Example 4

[0070] 1.3242 g of SrCO3, 0.0070 g of Bi2O3, and 0.4267 g of H3BO3 were weighed out respectively. The raw materials were mixed and placed in an agate mortar. Anhydrous ethanol was added at room temperature and the mixture was ground for 40 min. The mixture was then dried in a 90°C oven to obtain a mixed powder. The powder was placed in an alumina crucible and heated to 800°C at a rate of 5°C / min under atmospheric conditions for 2 hours to obtain a pre-calcined sample. The pre-calcined sample was then removed, ground, and placed in an alumina crucible. The temperature was increased to 1250°C at a rate of 5°C / min for 4 hours, followed by natural cooling to room temperature to obtain the product with the composition Sr3(BO3)2:Bi. 3+ The long-afterglow luminescent sample material was ground and then placed in a transparent test tube to test its luminescence properties.

[0071] Example 5

[0072] Weigh out 1.3242g of SrCO3 and 0.0051g of Pr6O, respectively. 11 Mix the above raw materials with 0.4267g H3BO3 and place them in an agate mortar. Add anhydrous ethanol at room temperature and grind for 40 min. Then dry in a 90℃ oven to obtain a mixed powder. Place the mixed powder in an alumina crucible and heat it to 800℃ at a heating rate of 5℃ / min under atmospheric conditions for 2 hours to obtain a pre-calcined sample. Remove the pre-calcined sample, grind it, and place it in an alumina crucible. Heat it to 1250℃ at a heating rate of 5℃ / min for 4 hours, and then cool it naturally to room temperature to obtain the product with the composition Sr3(BO3)2:Pr 3+ The long-afterglow luminescent sample material was ground and then placed in a transparent test tube to test its luminescence properties.

[0073] Example 6

[0074] 1.3242 g of SrCO3, 0.0052 g of CeO2, and 0.4267 g of H3BO3 were weighed out respectively. The raw materials were mixed and placed in an agate mortar. Anhydrous ethanol was added at room temperature and the mixture was ground for 40 min. The mortar was then dried in a 90°C oven to obtain a mixed powder. The mixed powder was placed in an alumina crucible and heated to 800°C at a rate of 5°C / min under atmospheric conditions for 2 hours to obtain a pre-calcined sample. The pre-calcined sample was then removed, ground, and placed in an alumina crucible. The temperature was increased to 1250°C at a rate of 5°C / min for 4 hours, and then allowed to cool naturally to room temperature to obtain the product with the composition Sr3(BO3)2:Ce. 4+ The long-afterglow luminescent sample material was ground and then placed in a transparent test tube to test its luminescence properties.

[0075] X-ray diffraction analysis was performed on the borate long-afterglow luminescent materials prepared in Examples 1-3 using a panalytical X'pert PRO X-ray powder diffractometer. The radiation source used was CuKα, with an operating voltage of 40 kV and an operating current of 40 kV. The scanning degree is 10-90 degrees. Figure 1 The XRD diffraction patterns and standard cards of the borate long afterglow luminescent materials prepared in Examples 1-3 of this invention are shown. The borate long afterglow luminescent materials prepared in Examples 1-3 of this invention are Ca3(BO3)2 crystal phase, which is consistent with the standard card (PDF#70-0868(Ca3(BO3)2)).

[0076] The excitation and emission spectra of the borate long-afterglow materials from Examples 1-3 were measured using a Thermo Scientific Lumina fluorescence spectrophotometer (the same instrument model is used throughout this document). Figure 2 The Bi-doped borate long afterglow luminescent material Ca3(BO3)2:Bi prepared in Example 1 3+ The excitation and emission spectra, Figure 5 The Pr-doped borate long afterglow luminescent material Ca3(BO3)2:Pr prepared in Example 2 3+ The excitation and emission spectra, Figure 8 The Ce-doped borate long afterglow luminescent material Ca3(BO3)2:Ce prepared in Example 3 4+ The excitation and emission spectra show that the Bi-doped sample exhibits a broad emission peak of 370-500 nm under 260.3 nm excitation, with the main peak located near 397.7 nm. The Pr-doped sample shows an emission spectrum with the main peak near 324 nm under 250.3 nm excitation, indicating ultraviolet light. The Ce-doped sample shows an emission spectrum with the main peak near 397 nm under 293.4 nm excitation, indicating violet light.

[0077] Afterglow spectra and afterglow decay curves were tested on the borate long afterglow materials of Examples 1-3. The results are shown in the figure. Figure 3 , 4 Numbers 6, 7, 9, and 10. Measurements were performed using a Horiba FluoroMax-4 X-ray source (the same model is used throughout). The operating voltage and current of the X-ray excitation source were 50 kV and 80 μA, respectively (the same model of X-ray source is used throughout), and the excitation time was 1 minute. Figure 3 As shown, the Bi-doped borate long afterglow luminescent material Ca3(BO3)2:Bi prepared in Example 1 3+ The main peak of the afterglow spectrum after X-ray excitation is located near 450 nm, exhibiting blue afterglow with strong intensity. Monitoring the attenuation curve at 441 nm... Figure 4 As shown, the results indicate that the afterglow time is much greater than 5400 s. Figure 6 As shown, the Pr-doped borate long afterglow luminescent material Ca3(BO3)2:Pr prepared in Example 2 3+ The main peak of the afterglow spectrum after X-ray excitation is located near 310 nm, which is ultraviolet afterglow and also has a strong afterglow intensity. Figure 9 As shown, the Ce-doped borate long afterglow luminescent material Ca3(BO3)2:Ce prepared in Example 3 4+The main peak of the afterglow spectrum is located near 400 nm, exhibiting a purple afterglow with strong afterglow intensity. The afterglow decay results demonstrate that the borate long-afterglow luminescent materials prepared in this invention all possess a relatively long afterglow duration.

[0078] Figure 11 The borate long-afterglow luminescent material Sr3(BO3)2:Bi prepared in Examples 4-6 3+ (Pr 3+ Ce 4+ According to the XRD diffraction pattern and standard card, the borate long afterglow luminescent materials prepared in Examples 4-6 are Sr3(BO3)2 crystal phase, which is consistent with the standard card (PDF#31-1343(Sr3(BO3)2)).

[0079] Figure 12 , 14 16 and 16 are the excitation and emission spectra of the borate long-afterglow materials in Examples 4-6, respectively. It can be seen that the Bi-doped borate long-afterglow luminescent material Sr3(BO3)2:Bi prepared in Example 4... 3+ The emission spectrum under 263.5 nm light excitation exhibits a broad emission peak of 370-550 nm, with the main peak located near 438.2 nm, exhibiting blue light. Example 5 prepared a Pr-doped borate long-afterglow luminescent material, Sr3(BO3)2:Pr. 3+ Under 302.3 nm light excitation, it exhibits two distinct emission peaks, with the main peak located near 610 nm, displaying red light. The Ce-doped borate long-afterglow luminescent material Sr3(BO3)2:Ce prepared in Example 6... 4+ Under 275.3nm light excitation, the broad emission peak of 350-580nm is located near 467nm, which is blue light.

[0080] Afterglow spectroscopy was performed on the borate long afterglow materials of Examples 4-6, and the results are shown in the figure. Figure 13 , 15 And 17. Bi-doped borate long afterglow luminescent material Sr3(BO3)2:Bi prepared in Example 4 3+ The main peak of the afterglow spectrum after X-ray excitation is located near 438 nm, exhibiting a blue afterglow with a certain intensity. Example 5 prepared a Pr-doped borate long-afterglow luminescent material, Sr3(BO3)2:Pr. 3+ The afterglow spectrum after X-ray excitation has multiple peaks, with the main peak located near 500 nm. The Ce-doped borate long afterglow luminescent material Sr3(BO3)2:Ce prepared in Example 6... 4+ The main peak of the afterglow spectrum after X-ray excitation is located near 450 nm, exhibiting a blue afterglow. The afterglow attenuation results are as follows: Figure 18As shown, the results indicate that the borate long afterglow luminescent material prepared in this invention has excellent afterglow performance.

[0081] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. The application of a borate luminescent material as an X-ray excited long-afterglow luminescent material, characterized in that, The preparation method of the material includes the following steps: Weigh out compounds containing M, B, and N according to the stoichiometric ratio of M3(BO3)2:N, mix them, add anhydrous ethanol, and grind to obtain a uniformly ground powder, where M = Ca or Sr; N = Bi. 3+ Pr 3+ or Ce 4+ ; The mixed powder is pre-calcined in air at 500-800℃ for 2-6 hours to obtain a pre-calcined product. The heating rate during pre-calcination is 3-5℃ / min. Before pre-calcination, the uniformly ground mixed powder is dried in an oven at 80-100℃ to remove anhydrous ethanol from the sample, so as to avoid the generation of carbon impurities during the calcination process, which would reduce the afterglow luminescence of the sample. The pre-calcined product is heated to 1000-1300℃ in a reducing atmosphere or air atmosphere and calcined for 4-10 hours. The heating rate during calcination is 3-5℃ / min. The product is then naturally cooled to room temperature in the furnace to obtain an X-ray excited borate long afterglow luminescent material.

2. The application according to claim 1, characterized in that, The compound containing M is a carbonate of M, the compound containing B is boric acid, and the compound containing N is an oxide of N.

3. The application according to claim 2, characterized in that, The M-containing compound is CaCO3 or SrCO3, and the N-containing compound is Bi2O3 or Pr6O. 11 Or CeO2.

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