CN111154483B - Silicate fluorescent powder and preparation method and application thereof - Google Patents
Silicate fluorescent powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides silicate fluorescent powder anda preparation method and application thereof. The chemical general formula of the fluorescent powder is KGa x(1‑) SiO 4 :xEu 3+ Wherein 0 <xIs less than 1. The excitation spectrum of the fluorescent powder is in the ultraviolet region, and Eu is changed 3+ The doping amount of the light source can realize the shift of the spectrum and further realize the change of the luminous color. No matter what the luminescent color of the sample is in the excited state, there is a green afterglow phenomenon when the excitation light source is removed. The invention also provides a preparation method of the fluorescent powder. The sample of the invention has abundant luminescence property, and can be used as a novel fluorescent material applied to the anti-counterfeiting field.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to silicate fluorescent powder and a preparation method and application thereof.
Background
In recent years, the phenomenon of counterfeit has become a global problem. Counterfeiting of counterfeit jewelry, luxury goods, certificates, banknotes, etc. will cause serious economic losses. Therefore, the anti-counterfeiting technology plays an important role in protecting personal and national interests. Among them, the fluorescence technology has the advantages of simple operation, convenient observation, low price, etc., and has become one of the most popular anti-counterfeiting technologies.
At present, the anti-counterfeiting material of the fluorescence technology mainly takes an organic molecular material as a main material, and the material is expensive and has poor heat resistance and is difficult to apply to various fields. And the current anti-counterfeiting material has single luminous color and is easy to forge. Therefore, it is very important to develop a fluorescent material having good stability and abundant luminescence properties.
Disclosure of Invention
The invention aims to provide silicate fluorescent powder and a preparation method and application thereof, and aims to solve the problems of high cost, poor thermal stability and single luminescent color of the existing luminescent material applied to the anti-counterfeiting field.
The technical scheme adopted by the invention for realizing the purpose is as follows: silicate fluorescent powder and preparation method thereofThe chemical formula is KGa x(1-) SiO 4 :xEu 3+ Wherein 0 <x＜1。
A preparation method of silicate fluorescent powder comprises the following steps:
a. according to the general chemical formula KGa x(1-) SiO 4 :xEu 3+ Respectively weighing corresponding compounds of K, ga, si and Eu as raw materials according to the stoichiometric ratio of the elements, wherein 0 & ltxLess than 1; mixing and grinding the weighed raw materials to obtain a mixture;
b. b, heating the mixture obtained in the step a to 1000-1300 ℃, preserving the heat for 1-10 hours, and then naturally cooling to room temperature;
c. and taking out the sample and grinding to obtain the silicate fluorescent powder.
In the step a, K carbonate, ga oxide, si oxide and Eu oxide are weighed as raw materials respectively.
In the step a, the grinding time is 10-30 minutes.
In step b, the temperature rise rate is 200 ℃/h.
In the step b, the sintering atmosphere is air.
In the step c, the grinding time is 10-30 minutes.
The application of the silicate fluorescent powder in preparing anti-counterfeiting materials.
The invention has the beneficial effects that:
the silicate fluorescent powder is prepared by a high-temperature solid phase method, has good thermal stability, and is prepared by changing Eu 3+ The doping concentration of (a) may enable spectral modulation in the visible range. The excitation spectrum of the fluorescent powder is in a deep ultraviolet region at 254nm, and the spectrum movement can be realized through the regulation and control of the matrix, so that the change of the luminescent color is realized.
The luminescent material has rich luminescent property, and afterglow is green no matter what color is when the luminescent material is excited. Is especially suitable for the field of anti-counterfeiting materials.
The preparation method is simple, the sintering temperature is low, and the material is non-toxic and harmless and has less environmental pollution.
Drawings
FIG. 1 shows KGaSiO 4 :0.8%Eu 3+ XRD pattern of the phosphor.
FIG. 2 shows KGaSiO 4 :0.8%Eu 3+ Emission spectra of the phosphors at different temperatures.
FIG. 3 shows KGa x(1-) SiO 4 :xEu 3+ Emission spectrum of the phosphor.
FIG. 4 shows KGa x(1-) SiO 4 :xEu 3+ Afterglow emission spectrum of the phosphor.
FIG. 5 shows KGa x(1-) SiO 4 :xEu 3+ Afterglow time spectrum of the phosphor.
Detailed Description
The following describes the preparation method of the self-excited phosphor of the present invention in detail with specific examples.
Example 1: KGa 0.992 SiO 4 :0.008Eu 3+ And (3) preparing the fluorescent powder.
According to KGa 0.992 SiO 4 :0.008Eu 3+ The stoichiometric ratio of each element in the composition is 0.6911g of potassium carbonate, 0.9297g of gallium oxide, 0.6008g of silicon dioxide and 0.0141g of europium oxide. Grinding the weighed carbonate and oxide uniformly, placing the ground carbonate and oxide into a corundum crucible, placing the crucible into a muffle furnace, carrying out heat treatment in air atmosphere, raising the temperature of the heat treatment from normal temperature to 1200 ℃ at the speed of 200 ℃/h, preserving the heat for 10 hours, then naturally cooling to room temperature, and grinding to obtain KGa 0.992 SiO 4 :0.008Eu 3+ And (4) fluorescent powder. The phosphor was characterized as shown in fig. 1 and 2. The luminescent intensity of the phosphor prepared in example 1 at different temperatures was tested, and the specific test results are shown in table 1.
Table 1:
example 2: KGa 0.998 SiO 4 :0.002Eu 3+ And (3) preparing the fluorescent powder.
According to KGa 0.998 SiO 4 :0.002Eu 3+ The stoichiometric ratio of each element in the solution is 0.6911g of potassium carbonate, 0.9353g of gallium oxide, 0.6008g of silicon dioxide and 0.0035g of europium oxide. Grinding the weighed carbonate and oxide uniformly, placing the ground carbonate and oxide into a corundum crucible, placing the crucible into a muffle furnace, carrying out heat treatment in air atmosphere, raising the temperature from normal temperature to 1300 ℃ at the speed of 200 ℃/h, preserving the heat for 6 hours, then naturally cooling to room temperature, and grinding to obtain KGa 0.998 SiO 4 :0.002Eu 3+ And (3) fluorescent powder.
Example 3: KGa 0.995 SiO 4 :0.005Eu 3+ And (3) preparing the fluorescent powder.
According to KGa 0.995 SiO 4 :0.005Eu 3+ The stoichiometric ratio of each element in the composition is 0.6911g of potassium carbonate, 0.9325g of gallium oxide, 0.6008g of silicon dioxide and 0.0088g of europium oxide. Grinding the weighed carbonate and oxide uniformly, placing the ground carbonate and oxide into a corundum crucible, placing the crucible into a muffle furnace, carrying out heat treatment in air atmosphere, raising the temperature from normal temperature to 1100 ℃ at the speed of 200 ℃/h, preserving the heat for 10 hours, then naturally cooling to room temperature, and grinding to obtain KGa 0.995 SiO 4 :0.005Eu 3+ And (4) fluorescent powder.
Example 4: KGa 0.985 SiO 4 :0.015Eu 3+ And (3) preparing the fluorescent powder.
According to KGa 0.985 SiO 4 :0.015Eu 3+ The stoichiometric ratio of each element in the composition is 0.6911g of potassium carbonate, 0.9231g of gallium oxide, 0.6008g of silicon dioxide and 0.0624g of europium oxide. Grinding the weighed carbonate and oxide uniformly, placing the ground carbonate and oxide in a corundum crucible, placing the crucible in a muffle furnace, carrying out heat treatment in air atmosphere, raising the temperature from normal temperature to 1200 ℃ at a speed of 200 ℃/h, preserving the temperature for 10 hours, then naturally cooling to room temperature, grinding to obtain KGa 0.985 SiO 4 :0.015Eu 3+ And (4) fluorescent powder.
Example 5: KGa 0.96 SiO 4 :0.04Eu 3+ And (3) preparing the fluorescent powder.
According to KGa 0.96 SiO 4 :0.04Eu 3+ The stoichiometric ratio of each element in the composition is 0.6911g of potassium carbonate, 0.8998g of gallium oxide, 0.6008g of silicon dioxide and 0.0704g of europium oxide. Grinding the weighed carbonate and oxide uniformly, placing the ground carbonate and oxide into a corundum crucible, placing the crucible into a muffle furnace, carrying out heat treatment in air atmosphere, raising the temperature of the heat treatment from normal temperature to 1200 ℃ at the speed of 200 ℃/h, preserving the heat for 10 hours, then naturally cooling to room temperature, and grinding to obtain KGa 0.96 SiO 4 :0.04Eu 3+ And (3) fluorescent powder.
Example 6: KGa 0.94 SiO 4 :0.06Eu 3+ And (3) preparing the fluorescent powder.
According to KGa 0.94 SiO 4 :0.06Eu 3+ The stoichiometric ratio of each element in the alloy is 0.6911g of potassium carbonate, 0.8808g of gallium oxide, 0.6008g of silicon dioxide and 0.1056g of europium oxide. Grinding the weighed carbonate and oxide uniformly, placing the ground carbonate and oxide into a corundum crucible, placing the crucible into a muffle furnace, carrying out heat treatment in air atmosphere, raising the temperature of the heat treatment from normal temperature to 1200 ℃ at the speed of 200 ℃/h, preserving the heat for 10 hours, then naturally cooling to room temperature, and grinding to obtain KGa 0.94 SiO 4 :0.06Eu 3+ And (3) fluorescent powder.
The phosphors prepared in examples 1 to 6 were tested for relative brightness, and the specific test results are shown in Table 2.
Table 2:
the phosphors prepared in examples 1 to 6 were subjected to a spectrum test, and the specific test results are shown in fig. 3.
Afterglow spectrum tests were performed on the phosphors prepared in examples 1 to 6, and the specific test results are shown in fig. 4.
Afterglow time tests were performed on the phosphors prepared in examples 1 to 6, and the specific test results are shown in fig. 5.
FIG. 1 shows that the phosphor of example 1 successfully synthesizes a pure phase material and has good crystallinity.
As shown in FIG. 2, the phosphor of example 1 has an emission peak in the green region at 503nm under the excitation of 254nm ultraviolet light. As the temperature increases, the intensity of luminescence increases first and then decreases to the maximum at 100 ℃. The emission peak is located in the red region at 618nm, and the luminous intensity gradually decreases with increasing temperature. It is because the two parts of the material emit light with different colors at different temperatures because the light intensity changes asynchronously.
As shown in FIG. 3, the emission spectra of the phosphors prepared according to examples 1-6 were varied. With increasing concentration, the peak at 503nm gradually decreased, and the characteristic peak at 618nm gradually increased. The product of the invention can be prepared by changing Eu 3+ The amount of doping of (a) achieves spectral modulation.
The phosphors prepared in examples 1 to 6 of the present invention all had an afterglow emission spectrum as shown in fig. 4. The afterglow emission spectrum of the product only detects a green light part but not a red light part, which shows that the afterglow of the series of materials is all green no matter how the luminescent color is under ultraviolet excitation.
The phosphors prepared in examples 1 to 6 of the present invention all had afterglow time spectra as shown in fig. 5. The product has different colors under ultraviolet excitation, can generate green afterglow emission, and has afterglow time of more than 1000s.
The above examples show that the preparation of the phosphor of the present invention can be carried out in air, and the prepared phosphor has good thermal stability and abundant luminescence properties. The method has good application prospect in the anti-counterfeiting field.
Claims (7)
1. The application of silicate fluorescent powder in preparing anti-counterfeiting material by utilizing green afterglow is characterized in that the silicate fluorescent powder has a chemical general formula of KGa x(1-) SiO 4 :xEu 3+ Wherein 0 <x＜1。
2. The use according to claim 1, wherein the preparation method of the silicate phosphor comprises the following steps:
a. according to the general chemical formula KGa x(1-) SiO 4 :xEu 3+ Respectively weighing corresponding compounds of K, ga, si and Eu as raw materials according to the stoichiometric ratio of the elements, wherein 0 & ltxLess than 1; mixing and grinding the weighed raw materials to obtain a mixture;
b. b, heating the mixture obtained in the step a to 1000-1300 ℃, preserving the heat for 1-10 hours, and then naturally cooling to room temperature;
c. and taking out the sample and grinding to obtain the silicate fluorescent powder.
3. The method as claimed in claim 2, wherein in step a, carbonate of K, oxide of Ga, oxide of Si, and oxide of Eu are weighed as raw materials.
4. Use according to claim 2, wherein in step a the milling time is 10-30 minutes.
5. The use according to claim 2, wherein in step b, the temperature is increased at a rate of 200 ℃/hr.
6. Use according to claim 2, wherein in step b the sintering atmosphere is air.
7. Use according to claim 2, wherein in step c the milling time is 10-30 minutes.
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| CN112175616B (en) * | 2020-10-30 | 2022-09-30 | 淮北师范大学 | Europium-doped potassium carbonate yttrium red fluorescent powder and preparation method thereof |
| CN112048298B (en) * | 2020-10-30 | 2022-09-09 | 淮北师范大学 | Potassium carbonate terbium fluorescent powder and preparation method thereof |
| CN116376538B (en) * | 2023-05-11 | 2024-04-19 | 广西师范大学 | Inorganic non-photochromic fluorescence-adjustable material doped with Eu ions in mixed valence state and preparation method thereof |
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| CN105713604A (en) * | 2016-01-25 | 2016-06-29 | 深圳市聚飞光电股份有限公司 | Preparation method of silicate fluorescent powder for LEDs |
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