CN116574509A - Multi-mode anti-counterfeiting fluorescent powder and preparation method thereof - Google Patents
Multi-mode anti-counterfeiting fluorescent powder and preparation method thereof Download PDFInfo
- Publication number
- CN116574509A CN116574509A CN202310551135.6A CN202310551135A CN116574509A CN 116574509 A CN116574509 A CN 116574509A CN 202310551135 A CN202310551135 A CN 202310551135A CN 116574509 A CN116574509 A CN 116574509A
- Authority
- CN
- China
- Prior art keywords
- fluorescent powder
- excitation
- luminescence
- counterfeiting
- furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000004020 luminiscence type Methods 0.000 claims abstract description 25
- 230000005284 excitation Effects 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 230000007704 transition Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7793—Germanates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a multi-mode anti-counterfeiting fluorescent powder, which has the characteristics of multi-mode excitation (white medium greenish under 254 and nm excitation, light pink under 365 and nm excitation), dynamic luminescence (the luminescence color under 265 and nm excitation is gradually changed from light pink to yellow-green) and afterglow luminescence (green). The chemical general formula of the fluorescent powder is xTb 3+ ,yEu 3+ :Mg 4‑x‑y Ga 4 Ge 3 O 16 X and y are mole fractions of corresponding elements, and x is more than or equal to 0.01 and less than or equal to 0.02,0.02, and y is more than or equal to 0.04. The preparation process comprises the following steps: weighing oxides of elements according to stoichiometric ratio, grinding and mixing uniformly; placing the mixture in a muffle furnace, roasting for 2-4 hours at 800-1000 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and grinding uniformly; and placing the obtained pre-prepared powder into a muffle furnace, roasting for 4-8 hours at 1200-1400 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and uniformly grinding to obtain the target fluorescent powder. The fluorescent powder has unique luminescence property, is difficult to imitate, and has higher safety and maximum in the advanced anti-counterfeiting fieldIs used for the application of the composition.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a multi-mode anti-counterfeiting fluorescent powder and a preparation method thereof.
Background
Counterfeit products (such as currency, branded goods, official documents, medicines and the like) have become a serious social problem in the past, and not only bring about great economic loss, but also bring about immeasurable risks to the safety and health of consumers. The development of advanced security materials to resist the spread of counterfeit products has become an urgent need for developing technology.
The fluorescent anti-counterfeiting method has the advantages of low production cost, simple design, environmental protection, difficult imitation and the like, and is an ideal anti-counterfeiting means for striking counterfeiters. The traditional fluorescent anti-counterfeiting material generally shows monochromatic light emission in a fixed excitation mode, has obvious anti-counterfeiting characteristics and is easy to imitate by counterfeiters, but if fluorescent materials with different colors are simply mixed, the anti-counterfeiting performance is possibly greatly reduced due to uneven dispersion. In order to improve the security level of anti-counterfeiting, researchers have developed different anti-counterfeiting modes of fluorescent materials, such as a multi-wavelength light response mode, a long afterglow mode and the like. The fluorescent material has the difficulty that different anti-counterfeiting modes are combined in the same matrix material, so that the fluorescent material is difficult to copy by counterfeiters, and has wide application prospect.
To date, there have been many reports and patents on multi-modal lighting strategies, principally in three respects: (1) The up-conversion luminescence and the down-conversion luminescence are combined, and the corresponding doped ions are induced to emit light through the excitation light with different wavelengths, so that the luminescence color is regulated; (2) Variable-temperature luminescence, wherein the luminescence color is regulated and controlled by utilizing the change of luminescence intensity of two or more rare earth ions at different temperatures; (3) The afterglow color-changing luminescence realizes the dynamic change of luminescence color by utilizing the afterglow service life difference of different doping ions. However, with the newer development of counterfeit technologies, the features of such counterfeit technologies are well known to counterfeiters and the development of new counterfeit materials is not trivial.
xTb provided by the invention 3+ , yEu 3+ :Mg 4-x-y Ga 4 Ge 3 O 16 The fluorescent powder has the characteristics of multimode excitation (white and medium greenish under 254 and nm excitation, light pink under 365 and nm excitation), dynamic luminescence (the luminescence color under 265 and nm excitation gradually changes from pink to yellow-green) and afterglow luminescence (green). The material with the luminous characteristic cannot be imitated by any substitute at present, so that the material has higher safety and great application potential in the advanced anti-counterfeiting field.
Disclosure of Invention
The invention provides a multi-mode anti-counterfeiting fluorescent powder and a preparation method thereof, wherein the fluorescent powder has the advantages of simple preparation process, low cost and special luminous characteristics.
The chemical general formula of the fluorescent powder provided by the invention is xTb 3+ , yEu 3+ : Mg 4-x-y Ga 4 Ge 3 O 16 Wherein x and y are mole fractions of corresponding elements: 0.01 X is more than or equal to 0.02,0.02, y is more than or equal to 0.04.
The preparation method of the fluorescent powder comprises the following steps:
(1) Weighing oxides of elements according to stoichiometric ratio, placing the oxides in a mortar, adding a proper amount of absolute ethyl alcohol, fully grinding, uniformly mixing, and placing in a drying oven for drying;
(2) And (3) placing the dried mixture in a muffle furnace, roasting for 2-4 hours at 800-1000 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and grinding uniformly to obtain a pre-powder.
(3) And placing the pre-prepared powder into a muffle furnace, roasting for 4-8 hours at 1200-1400 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and uniformly grinding to obtain the target fluorescent powder.
xTb prepared by the invention 3+ , yEu 3+ :Mg 4-x-y Ga 4 Ge 3 O 16 The fluorescent powder can not deliquesce when being placed in the air for a long time, and has special luminous characteristics: under 265 nm ultraviolet excitation, due to luminescence center (matrix defect, tb 3+ 、Eu 3+ ) There is obvious energy transfer between them, and the fluorescent powder is light pink (matrix defect luminescence and Eu) 3+ Mix of luminescence), orange (matrix defect luminescence with Tb) 3+ 、Eu 3+ Mix of luminescence) to yellow-green (matrix defect luminescence with Tb 3+ Mix of luminescence); after the excitation is stopped, the fluorescent powder presents green afterglow lasting for 3 min. The luminescent material can be widely applied to the fields of optical anti-counterfeiting, optical information storage and the like.
Drawings
FIG. 1 is an XRD pattern of the phosphor in the example.
FIG. 2 is an emission spectrum of the phosphor of the example under 254/365/nm excitation, and the inset is a photograph of a real object.
Fig. 3 and 4 are respectively a time-resolved spectrum and a color coordinate diagram of the phosphor powder under 265 nm excitation in the embodiment, and the inset is a photograph of a real object.
Detailed Description
In order to better explain the present invention, the following detailed description of specific embodiments thereof will be given with reference to the accompanying drawings. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Examples
The chemical general formula of the fluorescent powder is 0.01Tb 3+ , 0.02Eu 3+ :Mg 3.97 Ga 4 Ge 3 O 16 。
Selecting commercially available high purity Ka>3N）Tb 4 O 7 、Eu 2 O 3 、MgO、Ga 2 O 3 、GeO 2 Accurately weighing the raw materials (total amount is 20 g) according to a stoichiometric ratio, putting the raw materials into an agate mortar, adding a proper amount of absolute ethyl alcohol, fully grinding, uniformly mixing, and drying in a drying oven; placing the dried mixture into a corundum crucible, roasting 2 h in a muffle furnace at 1000 ℃, naturally cooling to room temperature along with the furnace, and uniformly grinding to obtain a pre-powder; and (3) placing the pre-prepared powder in a muffle furnace, roasting 4 h at 1300 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and uniformly grinding to obtain the target fluorescent powder.
Performing X-ray diffraction analysis on the obtained afterglow fluorescent powder, and matching the diffraction pattern with JCPDS 89-0829 standard card (see figure 1 for details), wherein the sample is Mg 4 Ga 4 Ge 3 O 16 Pure phase. Under the excitation of 254, nm and 365, nm, the sample presents different luminescent colors, and the emission spectrum and the physical diagram are shown in fig. 2. Under 265 nm excitation, the luminescence color of the sample shows continuous change from white powder to yellow to green, and the time resolution spectrum and the color coordinate diagram are shown in fig. 3 and 4.
Claims (3)
1. A multi-mode anti-counterfeiting fluorescent powder is characterized in that, features of multimode excitation (white-medium greenish under 254 nm excitation, light pink under 365 nm excitation), dynamic luminescence (gradual transition of luminescence color from light pink to yellowish green under 265 nm excitation), and afterglow luminescence (green) are presented.
2. The multi-modal anti-counterfeiting fluorescent powder according to claim 1, wherein the fluorescent powder has a chemical formula of xTb 3+ , yEu 3+ : Mg 4-x-y Ga 4 Ge 3 O 16 X and y are mole fractions of corresponding elements, and the range of the mole fractions is that x is more than or equal to 0.01 and less than or equal to 0.02,0.02 and y is more than or equal to 0.04.
3. The preparation method of the multi-mode anti-counterfeiting fluorescent powder is characterized by comprising the following steps of:
(1) Weighing oxides of elements according to stoichiometric ratio, grinding and mixing uniformly;
(2) Placing the mixture into a muffle furnace, roasting for 2-4 hours at 800-1000 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and uniformly grinding to obtain a pre-powder;
(3) And placing the pre-prepared powder into a muffle furnace, roasting for 4-8 hours at 1200-1400 ℃ in an oxidizing atmosphere, naturally cooling to room temperature along with the furnace, and uniformly grinding to obtain the target fluorescent powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310551135.6A CN116574509B (en) | 2023-05-16 | 2023-05-16 | Multi-mode anti-counterfeiting fluorescent powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310551135.6A CN116574509B (en) | 2023-05-16 | 2023-05-16 | Multi-mode anti-counterfeiting fluorescent powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116574509A true CN116574509A (en) | 2023-08-11 |
| CN116574509B CN116574509B (en) | 2023-11-17 |
Family
ID=87540835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310551135.6A Active CN116574509B (en) | 2023-05-16 | 2023-05-16 | Multi-mode anti-counterfeiting fluorescent powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116574509B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017257A (en) * | 1998-06-30 | 2000-01-18 | Nichia Chem Ind Ltd | Fluorescent substance and luminous screen using the same |
| CN101134895A (en) * | 2006-08-15 | 2008-03-05 | 大连路明科技集团有限公司 | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same |
| CN105255478A (en) * | 2015-10-15 | 2016-01-20 | 广东工业大学 | Reversible photochromic material with near-infrared long afterglow luminescence and preparing method thereof |
| WO2021099233A1 (en) * | 2019-11-18 | 2021-05-27 | Merck Patent Gmbh | Method for fabricating a particle |
| CN113201338A (en) * | 2021-03-18 | 2021-08-03 | 兰州大学 | Multi-modal luminescent anti-counterfeiting material and preparation method and application thereof |
-
2023
- 2023-05-16 CN CN202310551135.6A patent/CN116574509B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017257A (en) * | 1998-06-30 | 2000-01-18 | Nichia Chem Ind Ltd | Fluorescent substance and luminous screen using the same |
| CN101134895A (en) * | 2006-08-15 | 2008-03-05 | 大连路明科技集团有限公司 | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same |
| CN105255478A (en) * | 2015-10-15 | 2016-01-20 | 广东工业大学 | Reversible photochromic material with near-infrared long afterglow luminescence and preparing method thereof |
| WO2021099233A1 (en) * | 2019-11-18 | 2021-05-27 | Merck Patent Gmbh | Method for fabricating a particle |
| CN113201338A (en) * | 2021-03-18 | 2021-08-03 | 兰州大学 | Multi-modal luminescent anti-counterfeiting material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YIYU ZHAN ET AL.: "Cr3+-doped Mg4Ga4Ge3O16 near-infrared phosphor membrane for optical information storage and recording", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 777, pages 991 - 1000 * |
| 赖小辉: "若干铈、铽、锰掺杂镓酸盐余辉材料的制备及性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 02, pages 020 - 1285 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116574509B (en) | 2023-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Synthesis and luminescent properties of Ln3+ (Eu3+, Sm3+, Dy3+)-doped lanthanum aluminum germanate LaAlGe2O7 phosphors | |
| Wei et al. | Tunable emission and energy transfer in single-phased Ba9Lu2Si6O24: Bi3+, Eu3+ for UV W-LEDs | |
| Lu et al. | Synthesis and luminescence properties of double perovskite Ba2MgGe2O7: Mn4+ deep red phosphor | |
| CN114437724B (en) | Gallate-based multicolor long-afterglow luminescent material and preparation method thereof | |
| Tong et al. | Color tunable emission from CaS: Cu+, Mn2+ rare-earth-free phosphors prepared by a simple carbon-thermal reduction method | |
| CN106544021B (en) | The borate fluorescent powder and preparation method thereof that a kind of cerium, terbium are co-doped with | |
| CN112094647A (en) | Narrow-band emission nitrogen oxide red fluorescent powder and preparation method thereof | |
| CN105778913A (en) | Single-matrix triple-doped white fluorescent material and preparation method and application thereof | |
| CN113201338B (en) | Multi-modal luminescent anti-counterfeiting material and preparation method and application thereof | |
| CN100386405C (en) | Red long afterglow luminescent material and its prepn | |
| Kim et al. | The luminescence properties of M2MgSi2O7: Eu2+ (M= Sr, Ba) nano phosphor in ultraviolet light emitting diodes | |
| CN116574509B (en) | Multi-mode anti-counterfeiting fluorescent powder and preparation method thereof | |
| JP2013507455A (en) | Bismuth ion sensitized rare earth germanate luminescent material and method for producing the same | |
| CN101805609A (en) | Orange long afterglow phosphors in strontium stannate composite oxide system and preparation method thereof | |
| CN108276998B (en) | Trivalent samarium ion doped barium gadolinium titanate red fluorescent powder and preparation method thereof | |
| CN115926793A (en) | Multi-response anti-counterfeiting germanate fluorescent powder with adjustable luminescence color as well as preparation method and application thereof | |
| Shi et al. | Energy transfer effect in novel Sm3+-Eu3+ co-activated CaMgAl10O17 phosphors | |
| Liu et al. | Preparation and photoluminescence properties of Eu 3+ ion-doped Mg 2 LaTaO 6 phosphor | |
| CN104910916B (en) | A kind of glow color adjustable New Phosphorus lime stone structure light-emitting material and application thereof | |
| CN114456808A (en) | Tantalate-based red long-afterglow luminescent material and preparation method thereof | |
| CN106978174A (en) | A kind of tungsten boric acid lanthanum fluorescent material of doping and preparation method and application | |
| Zhong et al. | The self‐reduction synthesis and luminescent properties of Eu2+/Eu3+ activated BaZrxSi3O7+ 2x phosphors with white light emission for white light‐emitting diodes | |
| CN112812773A (en) | Luminescence-enhanced rare earth doped phosphate all-white fluorescent powder and preparation method thereof | |
| CN114479856B (en) | Luminescent material, preparation method and application thereof | |
| Pei et al. | Energy transfer, colour tuneable emissions and LED application of solid solution phosphors K2Y1-x-yTbxEuyZr (PO4) 3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |