CN113845913B - Garnet-based multimode fluorescent anti-counterfeiting material excited by blue light and preparation method thereof - Google Patents
Garnet-based multimode fluorescent anti-counterfeiting material excited by blue light and preparation method thereof Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 8
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Abstract
The invention relates to the technical field of rare earth luminescent optical information safety, in particular to a garnet-based multimode fluorescent anti-counterfeiting material excited by blue light and a preparation method thereof. The chemical formula of the material is as follows: caCd 2 Ga 2 Ge 3 O 12 ；xPr 3+ ,yH 3 BO 3 Wherein x is more than or equal to 0.002 and less than or equal to 0.003,0.02 and less than or equal to 0.06. The method is completed by the steps of raw material mixing, pre-sintering and sintering. The material can realize optical information identification under four luminescence modes of photoluminescence, afterglow luminescence, thermoluminescence and upconversion luminescence under the excitation of blue light, has the advantages of storage resistance, heat resistance and good crystallinity, has high afterglow luminescence intensity and long afterglow time, is stable, and can realize the preparation of a series of multi-mode luminescent materials. Can be used as an anti-counterfeiting material to be applied to the fields of trademark anti-counterfeiting and information encryption. The raw materials needed by the preparation material are cheap, the preparation process is simple and convenient, and large-scale equipment is not needed.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent optical information safety, in particular to a garnet-based multimode fluorescent anti-counterfeiting material excited by blue light and a preparation method thereof.
Background
With the rapid development of economy, the market transaction scale and resource informatization reach unprecedented heights, and along with the rapid development of economy, people face increasingly serious problems of counterfeit and counterfeiting and information security, so that the anti-counterfeiting and information security become the focus of attention of people, and the development and utilization of safe, convenient and efficient anti-counterfeiting and information storage technologies become increasingly urgent. Luminescent materials have received a great deal of attention in the fields of anti-counterfeiting and information encryption because of their special optical properties (multicolor emission, visual identification and simplicity and ease of operation).
The fluorescence anti-counterfeiting technology widely used in the market at present is a single or dual-mode photoluminescence technology, and the main research focuses on the fluorescence anti-counterfeiting excited by short wavelength. For example, the multicolor fluorescent anti-counterfeiting ink prepared in the application publication No. CN 112457718A can show photoluminescence of various colors under the excitation of 250nm-410 nm. For example, the dynamic color-changing flexible composite material prepared in application publication No. CN112940507A can realize the dynamic change of photoluminescence color under the excitation of ultraviolet light, thereby greatly improving the anti-counterfeiting level. For example, the aqueous anti-counterfeiting ink prepared in the application publication No. CN 112430462A is obtained by a fluorescent pigment, and finally, the photoluminescence anti-counterfeiting under the aqueous condition is realized. However, the currently researched fluorescent anti-counterfeiting materials are all based on photoluminescence, and one or two fluorescent anti-counterfeiting technologies with light-emitting modes are developed, so that the application range is narrow, counterfeiting and counterfeiting are easy to realize, especially, the fluorescent anti-counterfeiting technologies can be identified only under short-wavelength excitation, but the short-wavelength excitation conditions in production and life are difficult to create. The development of the multi-mode fluorescent anti-counterfeiting material excited by long wavelength can broaden the variety of the fluorescent anti-counterfeiting material and has better security performance.
Disclosure of Invention
Based on the technical problems of short excitation wavelength, single fluorescent anti-counterfeiting characteristic and the like of the anti-counterfeiting fluorescent material, the invention aims to provide a garnet-based multimode fluorescent anti-counterfeiting material excited by blue light and a preparation method thereof.
The invention provides a blue light-excited garnet-based multimode fluorescent anti-counterfeiting material, which has the chemical formula as follows: caCd 2 Ga 2 Ge 3 O 12 ；xPr 3+ ,yH 3 BO 3 Wherein x is more than or equal to 0.002 and less than or equal to 0.003,0.02 and less than or equal to 0.06.
Further, in the chemical formula of the blue light-excited garnet-based multimode fluorescent anti-counterfeiting material, y is 0.04, and when y is 0.04, the blue light-excited garnet-based multimode fluorescent anti-counterfeiting material has the optimal afterglow decay time and the best crystallinity.
The invention also discloses a preparation method of the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light, which comprises the following specific steps:
step one, weighing: with CaCO 3 、CdCO 3 、Ga 2 O 3 、GeO 2 And Pr 6 O 11 Weighing raw materials according to the composition of a chemical structural formula and a stoichiometric ratio, mixing, adding boric acid (H) with the mass percentage of 2-6% of the mixture of the 5 raw materials 3 BO 3 ) As fluxing agent, and the raw materials are mixed evenly and put into aluminaUniformly grinding in air in a crucible; wherein, pr is adopted 6 O 11 And H 3 BO 3 While participating in the reaction, pr 3+ And B 3+ Co-incorporated into the matrix structure, such that Pr 3+ Doping of H 3 BO 3 The melting assistant can reduce the material synthesis temperature, and the prepared garnet-based multimode fluorescent anti-counterfeiting material has better crystallinity, strong luminance and longer afterglow decay time;
step two, pre-sintering: heating the ground raw materials to 550 ℃ in an air atmosphere muffle furnace for presintering, keeping the temperature for 4 hours, and naturally cooling to room temperature, wherein the presintering aims to improve the crystallinity of the materials;
step three, sintering: grinding the material obtained by pre-sintering and cooling to room temperature, placing the ground material in an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving heat for 6 hours, and grinding the material obtained after cooling to room temperature to obtain the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light.
Further, in the step one, boric acid (H) with the mass percentage of the mixture of the above 5 materials being 4.0% is added 3 BO 3 ) As a fluxing agent, plays a decisive role in the singleness and stability of the crystal form.
The invention also protects the garnet-based multimode fluorescent anti-counterfeiting material excited by the blue light as an anti-counterfeiting material to be applied to the field of multimode luminous trademark anti-counterfeiting or information encryption.
Compared with the prior art, the invention has the following beneficial effects:
in a single garnet base CaCd 2 Ga 2 Ge 3 O 12 In the material, the preparation method of ion substitution, high-temperature sintering and cosolvent addition is adopted, and Pr can be changed 3+ And H 3 BO 3 And (4) preparing the garnet-based fluorescent anti-counterfeiting material. The material can realize multi-mode luminescence, pr 3+ And Ca 2+ /Cd 2+ The ionic radii of the ions are similar, solid solution substitution can be realized in high-temperature solid-phase reaction, and simultaneously, the ions can formDefects, multiple modes of luminescence, and final preparation of CaCd 2 Ga 2 Ge 3 O 12 ；Pr 3+ Fluorescent anti-counterfeiting material.
The material can realize optical information identification under four luminescence modes of photoluminescence, afterglow luminescence, thermoluminescence and upconversion luminescence under the excitation of blue light, has the advantages of storage resistance, heat resistance and good crystallinity, has high afterglow luminescence intensity and long afterglow time, is stable, and can realize the preparation of a series of multi-mode luminescent materials. Can be used as an anti-counterfeiting material to be applied to the fields of trademark anti-counterfeiting and information encryption. Wherein the matrix CaCd 2 Ga 2 Ge 3 O 12 It has the advantages of high temperature resistance, stable chemical property, no toxicity, etc. In the doped red luminescent center Pr 3+ On the basis of (1), adopt H 3 BO 3 As a cosolvent, materials with good crystallinity can be obtained, and the materials have stable chemical and physical properties and can be better applied to actual production. The raw materials needed by the preparation material are low in price, the preparation process is simple and convenient, and large-scale equipment is not needed; the prepared material has good water resistance and heat resistance. Therefore, the material has potential application value in the fields of trademark anti-counterfeiting and information encryption.
Drawings
FIG. 1 is an XRD spectrum of the fluorescent anti-counterfeit material prepared in examples 1-3 of the present invention;
FIG. 2 is an excitation spectrum of the fluorescent anti-counterfeit material prepared in example 2 of the present invention;
FIG. 3 is an emission spectrum of the anti-fluorescence anti-counterfeiting material prepared in example 2 of the present invention;
FIG. 4 is an afterglow spectrum of the anti-fluorescent anti-counterfeit material prepared in example 2 of the present invention;
FIG. 5 is an afterglow decay curve of the fluorescent anti-counterfeit material prepared in example 2 of the present invention;
FIG. 6 is a thermoluminescent spectrum of the fluorescent anti-counterfeit material prepared in example 2 of the present invention;
FIG. 7 is a light excitation spectrum of the fluorescent anti-counterfeit material prepared in example 2 of the present invention;
FIG. 8 is a topographical view of the fluorescent anti-counterfeit material prepared in example 2 of the present invention;
FIG. 9 is an afterglow decay curve of the fluorescent anti-counterfeit materials prepared in example 2 of the present invention and comparative examples 1 and 2;
FIG. 10 is an afterglow decay curve of the fluorescent anti-counterfeit materials prepared in example 2 of the present invention and comparative example 3.
Detailed Description
The technical solutions of the present invention will be described below clearly and completely in conjunction with the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a garnet-based multimode fluorescent anti-counterfeiting material excited by blue light comprises the following specific steps:
weighing CaCO 3 (4N)1mol、CdCO 3 (4N)2mol、Ga 2 O 3 (4N)1mol、GeO 2 (4N) 3mol and Pr 6 O 11 (4N) 0.00033mol, adding boric acid (H) with the mass percent of 4 percent of the 5 raw material mixtures 3 BO 3 (4N)) as a fluxing agent, uniformly mixing the raw materials, putting the mixture into an alumina crucible, and uniformly grinding the mixture in air; heating the ground raw materials to 550 ℃ in an air atmosphere muffle furnace for pre-sintering, keeping the temperature for 4 hours, and naturally cooling to room temperature; grinding the material obtained by pre-sintering and cooling to room temperature, putting the ground material into an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving the heat for 6h, grinding the material obtained after cooling to room temperature, and preparing the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light, wherein an XRD (X-ray diffraction) pattern of the garnet-based multimode fluorescent anti-counterfeiting material is shown in an attached figure 1, and a single phase is formed and the crystallinity is good.
Example 2
A preparation method of a garnet-based multimode fluorescent anti-counterfeiting material excited by blue light comprises the following specific steps:
weighing CaCO 3 (4N)1mol、CdCO 3 (4N)2mol、Ga 2 O 3 (4N)1mol、GeO 2 (4N) 3mol and Pr 6 O 11 (4N) 0.00042mol, adding boric acid (H) with the mass percent of 4 percent of the 5 raw material mixtures 3 BO 3 (4N)) as a fluxing agent, uniformly mixing the raw materials, putting the mixture into an alumina crucible, and uniformly grinding the mixture in air; heating the ground raw materials to 550 ℃ in an air atmosphere muffle furnace for pre-sintering, keeping the temperature for 4 hours, and naturally cooling to room temperature; and grinding the material obtained by pre-sintering and cooling to room temperature, putting the ground material into an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving heat for 6 hours, and grinding the material obtained after cooling to room temperature to obtain the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light.
The XRD pattern is shown in figure 1, and it can be seen that a single phase is formed and the crystallinity is good. The excitation spectrum is shown in figure 2, and the fluorescent anti-counterfeiting material has obvious absorption in a blue light region, can realize blue light emission and has blue light excitation performance. The emission spectrum is shown in figure 3, and it can be seen that the fluorescent anti-counterfeiting material shows obvious red luminescence under the excitation of blue light. The afterglow spectrum is shown in figure 4, and the long afterglow luminescence of the fluorescent anti-counterfeiting material shows obvious red luminescence. The afterglow decay curve is shown in figure 5, and the fluorescent anti-counterfeiting material has excellent long afterglow decay performance. The thermoluminescence spectrum is shown in figure 6, and the fluorescent anti-counterfeiting material has excellent thermoluminescence performance. The optical excitation spectrum is shown in figure 7, and the fluorescent anti-counterfeiting material has excellent optical excitation luminescence property. The appearance figure is shown in figure 8, and the fluorescent anti-counterfeiting material has excellent crystallinity.
Example 3
A preparation method of a garnet-based multimode fluorescent anti-counterfeiting material excited by blue light comprises the following specific steps:
weighing CaCO 3 (4N)1mol、CdCO 3 (4N)2mol、Ga 2 O 3 (4N)1mol、GeO 2 (4N) 3mol and Pr 6 O 11 (4N) 0.0005mol, adding boric acid (H) with the mass percent of 4% in the above 5 raw material mixture 3 BO 3 (4N)) as a helpFusing agent, mixing the above raw materials uniformly, putting into an alumina crucible, and grinding uniformly in air; heating the ground raw materials to 550 ℃ in an air atmosphere muffle furnace for pre-sintering, keeping the temperature for 4 hours, and naturally cooling to room temperature; grinding the material obtained by pre-sintering and cooling to room temperature, putting the ground material into an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving the heat for 6h, grinding the material obtained after cooling to room temperature, and preparing the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light, wherein an XRD (X-ray diffraction) pattern of the garnet-based multimode fluorescent anti-counterfeiting material is shown in an attached figure 1, and a single phase is formed and the crystallinity is good.
Comparative example 1
With reference to example 2, caCO was weighed 3 (4N)1mol、CdCO 3 (4N)2mol、Ga 2 O 3 (4N)1mol、GeO 2 (4N) 3mol and Pr 6 O 11 (4N) 0.00042mol, adding boric acid (H) with the mass percent of 2 percent of the 5 raw material mixtures 3 BO 3 (4N)) as a fluxing agent, uniformly mixing the raw materials, putting the mixture into an alumina crucible, and uniformly grinding the mixture in air; heating the ground raw materials to 550 ℃ in an air atmosphere muffle furnace for pre-sintering, keeping the temperature for 4 hours, and naturally cooling to room temperature; grinding the material obtained by pre-sintering and cooling to room temperature, placing the ground material in an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving the heat for 6h, grinding the obtained material after cooling to room temperature to obtain the blue light excited garnet-based multimode fluorescent anti-counterfeiting material, wherein the decay curve of the rest glow is shown in figure 9, and the decay time of the afterglow can be seen to be reduced.
Comparative example 2
With reference to example 2, caCO was weighed 3 (4N)1mol、CdCO 3 (4N)2mol、Ga 2 O 3 (4N)1mol、GeO 2 (4N) 3mol and Pr 6 O 11 (4N) 0.00042mol, adding boric acid (H) with the mass percent of 6 percent of the 5 raw material mixtures 3 BO 3 (4N)) as a fluxing agent, uniformly mixing the raw materials, putting the mixture into an alumina crucible, and uniformly grinding the mixture in air; the above ground raw materials were put in a muffle furnace in an air atmosphere and heatedPre-sintering at 550 ℃ for 4h, and naturally cooling to room temperature; grinding the material obtained by pre-sintering and cooling to room temperature, placing the ground material in an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving the heat for 6h, grinding the obtained material after cooling to room temperature to obtain the blue light excited garnet-based multimode fluorescent anti-counterfeiting material, wherein the decay curve of the rest glow is shown in figure 9, and the decay time of the afterglow can be seen to be reduced.
Comparative example 3
Weighing CaCO according to example 2 3 (4N)1mol、CdCO 3 (4N)2mol、Ga 2 O 3 (4N)1mol、GeO 2 (4N) 3mol and Pr 6 O 11 (4N) 0.00042mol, adding boric acid (H) with the mass percent of 6 percent of the 5 raw material mixtures 3 BO 3 (4N)) as a fluxing agent, uniformly mixing the raw materials, putting the mixture into an alumina crucible, heating the mixture to 1050-1250 ℃ in an air atmosphere muffle furnace, sintering the mixture, keeping the temperature for 6 hours, cooling the mixture to room temperature, grinding the obtained material to prepare the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light, wherein the attenuation curve of the residual glow is shown in figure 10, and the reduction of the afterglow attenuation time can be seen.
Example 4
1g of each of the materials obtained in examples 1 to 3 and comparative examples 1 to 3 was spread on an open petri dish, and then stored in a constant temperature and humidity chamber at a temperature of 100 ℃ and a relative humidity of 70%. The afterglow time was measured after the end of month 2, and the results are shown in Table 1.
TABLE 1 comparison of decay times of afterglow of materials prepared in examples and comparative examples
Table 1 shows that: the afterglow decay time of the material obtained by the embodiment of the invention is stable and basically unchanged in the storage process. The materials obtained in the comparative examples 1-3 have obvious attenuation, which shows that the technical scheme of the invention obtains good technical effect and obtains the long afterglow material with the afterglow attenuation time not changing along with the storage time.
Example 5
1g of each of the materials obtained in examples 1 to 3 and comparative examples 1 to 3 was spread on an open petri dish, and then stored in a constant temperature and humidity chamber at a temperature of 30 ℃ and a relative humidity of 65%. At the end of month 2, the appearance was observed and measured, and the results are shown in Table 2.
TABLE 2 comparison of the appearance of the materials obtained in the examples with that of the comparative examples
| Appearance of 0 day pack | End of |
|
| Example 1 | Uniform particles without agglomeration | Uniform particles without agglomeration |
| Example 2 | Uniform particles without agglomeration | Uniform particles without agglomeration |
| Example 3 | Uniform particles without agglomeration | Uniform particles without agglomeration |
| Comparative example 1 | Uniform particles without agglomeration | Has obvious agglomeration |
| Comparative example 2 | Uniform particles without agglomeration | Has obvious agglomeration |
| Comparative example 3 | Uniform particles without agglomeration | Has obvious agglomeration |
Table 2 shows that: the material obtained by the embodiment of the invention is not easy to agglomerate in the storage process, and the appearance is kept in a stable state. The materials in the comparative examples 1-3 are obviously agglomerated, so that the addition of boric acid (cosolvent) with different contents can well avoid the agglomeration phenomenon of the obtained materials in the storage process; comparative example 3 had significant agglomeration, indicating that pre-sintering could also avoid agglomeration of the material.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. The garnet-based multimode fluorescent anti-counterfeiting material excited by blue light is characterized in that: the blue light-excited garnet-based multimode fluorescent anti-counterfeiting material has the chemical formula: caCd 2 Ga 2 Ge 3 O 12 ；xPr 3+ ，yH 3 BO 3 Wherein x is more than or equal to 0.002 and less than or equal to 0.003,0.02 and less than or equal to 0.06.
2. The garnet-based multimode fluorescent anti-counterfeiting material excited by blue light according to claim 1, characterized in that: in the chemical formula of the garnet-based multimode fluorescent anti-counterfeiting material excited by the blue light, y is 0.04.
3. The method for preparing the garnet-based multimode fluorescent anti-counterfeiting material excited by the blue light according to claim 1, which is characterized by comprising the following steps: the method comprises the following specific steps:
step one, weighing: with CaCO 3 、CdCO 3 、Ga 2 O 3 、GeO 2 And Pr 6 O 11 Weighing raw materials according to the composition of a chemical structural formula and a stoichiometric ratio, mixing, adding H accounting for 2-6% of the mass percent of the mixture of the 5 raw materials 3 BO 3 As fluxing agent, and the raw materials are mixed evenly and then put into an alumina crucible and ground evenly in the air;
step two, pre-sintering: heating the ground raw materials to 550 ℃ in an air atmosphere muffle furnace for pre-sintering, keeping the temperature for 4 hours, and naturally cooling to room temperature;
step three, sintering: grinding the material obtained by pre-sintering and cooling to room temperature, placing the ground material in an alumina crucible, heating to 1050-1250 ℃ in an air atmosphere muffle furnace for sintering, preserving heat for 6 hours, and grinding the material obtained after cooling to room temperature to obtain the garnet-based multimode fluorescent anti-counterfeiting material excited by blue light.
4. The preparation method of the blue-light-excited garnet-based multimode fluorescent anti-counterfeiting material according to claim 3, which is characterized by comprising the following steps: in the step one, H with the mass percent of the mixture of the 5 materials being 4.0 percent is added 3 BO 3 Acting as a fluxing agent.
5. The application of the blue-light-excited garnet-based multimode fluorescent anti-counterfeiting material as claimed in claim 1, is characterized in that: the garnet-based multimode fluorescent anti-counterfeiting material excited by the blue light is used as an anti-counterfeiting material and applied to the field of multimode luminous trademark anti-counterfeiting or information encryption.
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| CN110885682A (en) * | 2019-12-16 | 2020-03-17 | 武汉工程大学 | Gallate long afterglow fluorescent powder material and its preparation method |
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| Pr3+掺杂的Cd3M2Ge3O12(M = Al , Ga) 石榴石的阴极射线发光特性;田军;《硅酸盐学报》;19940831;第22卷(第4期);全文 * |
| 三价镧系离子掺杂的Cd3Al2Ge3O12 的长余辉发光;刘正伟;《发光学报》;20050430;第26卷(第2期);全文 * |
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