Magnesium strontium europium dysprosium silicate blue light-emitting material and preparation method thereof
By combining the sol-gel method with doping modification, the problem of coarse grains caused by the high-temperature solid-phase method was solved, and a magnesium strontium europium dysprosium blue light-emitting material with uniform composition, high purity and fine particles was prepared, which improved the luminous brightness.
Patent Information
- Application Number
- CN202510882540.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-27
- Publication Date
- 2025-10-10
AI Technical Summary
In the prior art, when synthesizing silicate long afterglow luminescent materials by a high-temperature solid-phase method, the crystal grains are coarse and the luminous brightness is greatly reduced after grinding.
The sol-gel method is combined with the doping modification method to prepare magnesium strontium europium dysprosium silicate blue light luminescent material by controlling the reaction conditions and the dopant ratio, thereby reducing the sintering temperature and improving the uniformity and fine particle size of the material.
A long afterglow luminescent material with uniform composition, high purity and fine particles was prepared, which improved the afterglow performance.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of long afterglow luminescent materials, and in particular to a magnesium strontium silicate europium dysprosium blue light luminescent material and a preparation method thereof. Background Art
[0002] Traditional long-lasting luminescent materials are mainly based on sulfides. Due to the poor chemical stability of sulfides, research on aluminate long-lasting luminescent materials has been conducted since the 1960s, and significant progress has been made. Since the silicate system has better compatibility with traditional ceramics and glass, research on silicate-based luminescent materials has been carried out. As silicate materials are the matrix of luminescent materials, the interaction energy between the luminescent center and the matrix is low, which allows the luminescent center ions to directly absorb the excitation energy, which is conducive to improving the luminescence efficiency. 2+ It has a long history of application as an activator in alkaline earth silicate systems. 2+ , Dy 3+ The system is a typical representative of silicate long-afterglow luminescent materials. Compared with aluminate-based long-afterglow materials, it has low cost and good water resistance, and has attracted widespread attention from researchers.
[0003] The most studied method at present is the high-temperature solid-phase method, but the high-temperature solid-phase method has the disadvantages of high synthesis temperature and difficulty in obtaining single-phase compounds. In addition, the grains are coarse, and the luminescence brightness will be greatly reduced after grinding. Summary of the Invention
[0004] The purpose of the present invention is to provide a magnesium strontium silicate europium dysprosium blue light luminescent material and a preparation method thereof, so as to solve the technical problem in the prior art that the high temperature solid phase method has coarse grains and the luminous brightness is greatly reduced after grinding.
[0005] The present invention discloses a method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material, comprising the following steps: S1. Dissolve tetraethyl orthosilicate in anhydrous ethanol to form a tetraethyl orthosilicate ethanol solution, dissolve an inorganic salt of strontium in anhydrous ethanol to form an ethanol solution A, dissolve an inorganic salt of magnesium in anhydrous ethanol to form an ethanol solution B, dissolve an inorganic salt of europium in anhydrous ethanol to form an ethanol solution C, and dissolve an inorganic salt of dysprosium in anhydrous ethanol to form an ethanol solution D; S2. According to the molar ratio of (strontium + europium): magnesium: (silicon + dysprosium) of 2:1:2, ethanol solution A, ethanol solution B, ethanol solution C and ethanol solution D were added to the ethanol solution of tetraethyl orthosilicate; S3. After adding nitric acid and water, the sol is allowed to stand to fully gel; S4. The gel obtained in step S3 is dried and then heat-treated in a reducing atmosphere.
[0006] Furthermore, the inorganic salt of strontium is Sr(NO3)2 or SrCl2; the inorganic salt of magnesium is Mg(NO3)2, MgCl2; the inorganic salt of europium is Eu(NO3)3·6H2O or EuCl2; and the inorganic salt of dysprosium is Dy(NO3)3·5H2O or DyCl3·6H2O.
[0007] Furthermore, the strontium concentration in the ethanol solution A is 0.5-0.8 mol / L; the magnesium concentration in the ethanol solution B is 0.5-0.8 mol / L; the europium concentration in the ethanol solution C is 0.1-0.3 mol / L; and the dysprosium concentration in the ethanol solution D is 0.1-0.3 mol / L.
[0008] Furthermore, the concentration of the tetraethyl orthosilicate ethanol solution is 0.5 mol / L-1.0 mol / L.
[0009] Furthermore, the addition amount of the nitric acid is H + :Si 4+ The molar ratio is 1:20 to 1:10.
[0010] Furthermore, the standard for adding water in step S3 is that the molar ratio of silicon to water is 1:6 to 1:4.
[0011] Furthermore, the drying temperature is 80-100°C.
[0012] Furthermore, the reducing atmosphere heat treatment temperature is 900-1100°C.
[0013] Furthermore, the heating rate of the reducing atmosphere heat treatment is 5°C / min, and the holding time is 1-2h.
[0014] A magnesium silicate strontium europium dysprosium blue light luminescent material, the molecular formula of which is: Sr （2-x） Eu x MgSi （2-y） Dy y O7, where the value of x is 0.01-0.05 and the value of y is 0.01-0.05.
[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention reduces the content of magnesium silicate strontium europium dysprosium blue light emitting material Sr2MgSi2O7: Eu 2+ , Dy 3+ By reducing the sintering temperature, a long afterglow luminescent material with uniform composition, high purity and fine particles is prepared, thereby improving the afterglow performance. DETAILED DESCRIPTION
[0016] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.
[0017] Example 1 This embodiment discloses a magnesium strontium silicate europium dysprosium blue light luminescent material and a preparation method thereof, comprising the following steps: Step 1: Weigh 0.5 mol of tetraethyl orthosilicate, 0.5 mol of Mg(NO3)2, and 0.5 mol of Sr(NO3)2 respectively, and dissolve them in 1 L of anhydrous ethanol to form an anhydrous ethanol solution of tetraethyl orthosilicate, magnesium nitrate and strontium nitrate with a concentration of 0.5 mol / L; weigh 0.01 mol of Eu(NO3)3·6H2O and 0.01 mol of Dy(NO3)3·5H2O respectively and dissolve them in 0.1 L of anhydrous ethanol to form an ethanol solution of europium nitrate and dysprosium nitrate with a total concentration of 0.1 mol / L.
[0018] Step 2: Take 398 ml of ethyl orthosilicate ethanol solution and place it in a beaker. Add 200 ml of magnesium nitrate ethanol solution, 398 ml of strontium nitrate ethanol solution, 10 ml of europium nitrate ethanol solution and 10 ml of dysprosium nitrate ethanol solution while stirring, add 0.01 mol of nitric acid, and then add 1 mol of water.
[0019] Step 3: The sol was allowed to stand for 24 hours to fully gel and then dried in an oven at 80°C. Then, it was placed in a hydrogen furnace and heated to 1100°C at a heating rate of 5°C / min and kept warm for 1 hour to obtain Sr 1.99 Eu 0.01 MgSi 1.99 Dy 0.01 O7 powder; finally, afterglow performance test is performed.
[0020] Example 2 Step 1: Weigh 0.5 mol of tetraethyl orthosilicate, 0.5 mol of Mg(NO3)2, and 0.5 mol of Sr(NO3)2 respectively, and dissolve them in 1 L of anhydrous ethanol to form an anhydrous ethanol solution of tetraethyl orthosilicate, magnesium nitrate and strontium nitrate with a concentration of 0.5 mol / L; weigh 0.01 mol of Eu(NO3)3·6H2O and 0.01 mol of Dy(NO3)3·5H2O respectively and dissolve them in 0.1 L of anhydrous ethanol to form an ethanol solution of europium nitrate and dysprosium nitrate with a total concentration of 0.1 mol / L.
[0021] Step 2: Take 396 ml of ethyl silicate ethanol solution in a beaker, add 200 ml of magnesium nitrate ethanol solution, 396 ml of strontium nitrate ethanol solution, 20 ml of europium nitrate ethanol solution and 20 ml of dysprosium nitrate ethanol solution in the process of stirring, add 0.01 mol of nitric acid, and then add 1 mol of water.
[0022] Step 3: The sol is placed in an oven at 80°C for drying after being left for 24 hours to fully gel, and then placed in a hydrogen furnace to heat to 1100°C at a heating rate of 5°C / min, and kept for 1 hour to obtain Sr 1.98 Eu 0.02 MgSi 1.98 Dy 0.02 O7 powder; finally, the afterglow performance test is carried out.
[0023] Example 3 Step 1: Respectively take 0.5 mol of ethyl silicate, 0.5 mol of Mg(NO3)2, 0.5 mol of Sr(NO3)2, and dissolve in 1L of anhydrous ethanol to form a concentration of 0.5 mol / L of ethyl silicate, magnesium nitrate and strontium nitrate anhydrous ethanol solution; Respectively take 0.01 mol of Eu(NO3)3·6H2O and 0.01 mol of Dy(NO3)3·5H2O and dissolve in 0.1L of anhydrous ethanol to form a total concentration of 0.1 mol / L of europium nitrate and dysprosium nitrate ethanol solution.
[0024] Step 2: Take 394 ml of ethyl silicate ethanol solution in a beaker, add 200 ml of magnesium nitrate ethanol solution, 394 ml of strontium nitrate ethanol solution, 30 ml of europium nitrate ethanol solution and 30 ml of dysprosium nitrate ethanol solution in the process of stirring, add 0.01 mol of nitric acid, and then add 1 mol of water.
[0025] Step 3: The sol is placed in an oven at 80°C for drying after being left for 24 hours to fully gel, and then placed in a hydrogen furnace to heat to 1100°C at a heating rate of 5°C / min, and kept for 1 hour to obtain Sr 1.97 Eu 0.03 MgSi 1.97 Dy 0.03 O7 powder; finally, the afterglow performance test is carried out.
[0026] Example 4 Step 1: Weigh 0.5 mol of tetraethyl orthosilicate, 0.5 mol of Mg(NO3)2, and 0.5 mol of Sr(NO3)2 respectively, and dissolve them in 1 L of anhydrous ethanol to form an anhydrous ethanol solution of tetraethyl orthosilicate, magnesium nitrate and strontium nitrate with a concentration of 0.5 mol / L; weigh 0.01 mol of Eu(NO3)3·6H2O and 0.01 mol of Dy(NO3)3·5H2O respectively and dissolve them in 0.1 L of anhydrous ethanol to form an ethanol solution of europium nitrate and dysprosium nitrate with a total concentration of 0.1 mol / L.
[0027] Step 2: Take 392 ml of ethyl orthosilicate ethanol solution and place it in a beaker. Add 200 ml of magnesium nitrate ethanol solution, 392 ml of strontium nitrate ethanol solution, 40 ml of europium nitrate ethanol solution and 40 ml of dysprosium nitrate ethanol solution while stirring, add 0.01 mol of nitric acid, and then add 1 mol of water.
[0028] Step 3: The sol was allowed to stand for 24 hours to fully gel and then dried in an oven at 80°C. Then, it was placed in a hydrogen furnace and heated to 1100°C at a heating rate of 5°C / min and kept warm for 1 hour to obtain Sr 1.96 Eu 0.04 MgSi 1.96 Dy 0.04 O7 powder; finally, afterglow performance test is performed.
[0029] Example 5 Step 1: Weigh 0.5 mol of tetraethyl orthosilicate, 0.5 mol of Mg(NO3)2, and 0.5 mol of Sr(NO3)2 respectively, and dissolve them in 1 L of anhydrous ethanol to form an anhydrous ethanol solution of tetraethyl orthosilicate, magnesium nitrate and strontium nitrate with a concentration of 0.5 mol / L; weigh 0.01 mol of Eu(NO3)3·6H2O and 0.01 mol of Dy(NO3)3·5H2O respectively and dissolve them in 0.1 L of anhydrous ethanol to form an ethanol solution of europium nitrate and dysprosium nitrate with a total concentration of 0.1 mol / L.
[0030] Step 2: Take 398 ml of ethyl orthosilicate ethanol solution and place it in a beaker. Add 200 ml of magnesium nitrate ethanol solution, 396 ml of strontium nitrate ethanol solution, 10 ml of europium nitrate ethanol solution and 20 ml of dysprosium nitrate ethanol solution while stirring, add 0.01 mol of nitric acid, and then add 1 mol of water.
[0031] Step 3: The sol was allowed to stand for 24 hours to fully gel and then dried in an oven at 80°C. Then, it was placed in a hydrogen furnace and heated to 1100°C at a heating rate of 5°C / min and kept warm for 1 hour to obtain Sr 1.99 Eu 0.01 MgSi 1.98 Dy 0.02O7 powder; finally, afterglow performance test is performed.
[0032] Comparative Example 1 The only difference between this comparative example and Example 1 is that the amount of ethyl orthosilicate used in step 2 is 418 ml.
[0033] Comparative Example 2 The only difference between this comparative example and Example 1 is that the amount of water added in step 2 is 0.5 mol.
[0034] Comparative Example 3 The only difference between this comparative example and Example 1 is that the sintering temperature in step 3 is 1200°C.
[0035] The key parameters and afterglow performance test results of the embodiment of the present invention are detailed in Table 1.
[0036] Table 1
[0037] The test results show that the central wavelength of all examples is 466nm, indicating that the prepared samples are pure and free of other crystalline phases. The afterglow time increases with increasing europium and dysprosium doping levels, and all exceed 20 hours, demonstrating excellent afterglow performance at all doping levels. In Comparative Example 1, the molar ratio of (strontium + europium): magnesium: (silicon + dysprosium) deviates from 2:1:2, resulting in a shift in the central wavelength, indicating the formation of other impurities. In Comparative Example 2, the afterglow time decreases due to insufficient water addition, and in Comparative Example 3, the afterglow time decreases due to excessively high sintering temperatures, indicating that afterglow performance deteriorates when deviating from the optimal experimental range.
[0038] The above are the implementation methods listed in this embodiment, but this embodiment is not limited to the above optional implementation methods. Those skilled in the art can arbitrarily combine the above methods to obtain other various implementation methods. Anyone can derive other various forms of implementation methods based on the inspiration of this embodiment. The above specific implementation methods should not be understood as limiting the scope of protection of this embodiment. The scope of protection of this embodiment shall be based on the definition in the claims, and the description can be used to interpret the claims.
Claims
1. A method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material, characterized in that: The following steps are included: S1. The inorganic salt of strontium is dissolved in anhydrous ethanol to form an ethanol solution A, the inorganic salt of magnesium is dissolved in anhydrous ethanol to form an ethanol solution B, the inorganic salt of europium is dissolved in anhydrous ethanol to form an ethanol solution C, and the inorganic salt of dysprosium is dissolved in anhydrous ethanol to form an ethanol solution D; S2. Add ethanol solution A, ethanol solution B, ethanol solution C, and ethanol solution D to the ethyl orthosilicate ethanol solution in a molar ratio of strontium + europium: magnesium: silicon + dysprosium of 2:1:2; S3. After adding nitric acid and water, the sol is allowed to stand to fully gel; S4. The gel obtained in step S3 is dried and then heat-treated in a reducing atmosphere.
2. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The inorganic salt of strontium is Sr(NO3)2 or SrCl2; the inorganic salt of magnesium is Mg(NO3)2 or MgCl2; the inorganic salt of europium is Eu(NO3)3·6H2O or EuCl2; and the inorganic salt of dysprosium is Dy(NO3)3·5H2O or DyCl3·6H2O.
3. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The strontium concentration in the ethanol solution A is 0.5-0.8 mol / L; the magnesium concentration in the ethanol solution B is 0.5-0.8 mol / L; the europium concentration in the ethanol solution C is 0.1-0.3 mol / L; and the dysprosium concentration in the ethanol solution D is 0.1-0.3 mol / L.
4. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The concentration of the tetraethyl orthosilicate ethanol solution is 0.5 mol / L-1.0 mol / L.
5. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The addition amount of nitric acid is H + :Si 4+ The molar ratio is 1:20 to 1:
10.
6. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The standard for adding water in step S3 is that the molar ratio of silicon to water is 1:6 to 1:
4.
7. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The drying temperature is 80-100°C.
8. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The reducing atmosphere heat treatment temperature is 900-1100°C.
9. The method for preparing a magnesium strontium silicate europium dysprosium blue light luminescent material according to claim 1, characterized in that: The heating rate of the reducing atmosphere heat treatment is 5°C / min, and the holding time is 1-2h.
10. A magnesium strontium silicate europium dysprosium blue light luminescent material, characterized by: Its molecular formula is: Sr （2-x） Eu x MgSi （2-y） Dy y O7, where the value of x is 0.01-0.05 and the value of y is 0.01-0.05.