CN113061432A - A kind of preparation method and application of high stability multifunctional monetite type phosphor - Google Patents
A kind of preparation method and application of high stability multifunctional monetite type phosphor Download PDFInfo
- Publication number
- CN113061432A CN113061432A CN202110367103.1A CN202110367103A CN113061432A CN 113061432 A CN113061432 A CN 113061432A CN 202110367103 A CN202110367103 A CN 202110367103A CN 113061432 A CN113061432 A CN 113061432A
- Authority
- CN
- China
- Prior art keywords
- whitlockite
- multifunctional
- fluorescent powder
- stability
- highly stable
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 9
- CVPJXKJISAFJDU-UHFFFAOYSA-A nonacalcium;magnesium;hydrogen phosphate;iron(2+);hexaphosphate Chemical compound [Mg+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Fe+2].OP([O-])([O-])=O.OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CVPJXKJISAFJDU-UHFFFAOYSA-A 0.000 claims description 19
- 229910052591 whitlockite Inorganic materials 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 1
- 230000008635 plant growth Effects 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 238000010532 solid phase synthesis reaction Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 9
- 238000007639 printing Methods 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 12
- 239000011707 mineral Substances 0.000 description 12
- 235000010755 mineral Nutrition 0.000 description 12
- 239000000976 ink Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 230000002265 prevention Effects 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000036541 health Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004891 communication Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003862 health status Effects 0.000 description 3
- 238000001483 high-temperature X-ray diffraction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052611 pyroxene Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 208000025721 COVID-19 Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 208000016169 Fish-eye disease Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- -1 Mn2+ ions Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000013474 audit trail Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 210000001525 retina Anatomy 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004861 thermometry Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7723—Phosphates
- C09K11/7724—Phosphates with alkaline earth metals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
- B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ecology (AREA)
- Forests & Forestry (AREA)
- Environmental Sciences (AREA)
- Botany (AREA)
- Inorganic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Wood Science & Technology (AREA)
- Luminescent Compositions (AREA)
- Credit Cards Or The Like (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
本发明公开了一种高稳定性多功能白磷钙石型荧光粉的制备方法及应用，化学式为(Ca0.5Sr0.5)3‑yM0.07(PO4)2:0.07Ce3+,yMn2+，y的取值为0,0.01,0.03,0.05,0.07,0.09,0.11，M为碱性金属。本发明具备良好的热稳定性和化学稳定性，实现550‑720nm红光、720‑900nm近红外光的光谱激发显色，颜色从紫色可调谐至红色，可被制成特定波长激发的防伪油墨，在防伪图案、手机快速响应二维码的印制、近红外生物应用和场致发射显示潜在的应用前景。
The invention discloses a preparation method and application of a high - stability multifunctional monetite type fluorescent powder . , the value of y is 0, 0.01, 0.03, 0.05, 0.07, 0.09, 0.11, and M is an alkaline metal. The invention has good thermal stability and chemical stability, realizes the spectral excitation color development of 550-720nm red light and 720-900nm near-infrared light, the color can be tuned from purple to red, and can be made into anti-counterfeiting ink excited by a specific wavelength , showing potential application prospects in anti-counterfeiting patterns, mobile phone rapid response two-dimensional code printing, near-infrared biological applications and field emission.
Description
Technical Field
The invention belongs to the technical field of fluorescent powder preparation, and particularly relates to a preparation method and application of high-stability multifunctional whitlockite fluorescent powder.
Background
Human perception of the luminescence of materials begins with the luminescence of natural minerals. The mineral luminescent materials can be divided into two categories: firstly, natural mineral luminescent material; the second is artificially synthesized luminescent material with mineral structure. The natural mineral usually contains rare earth quencher ions, and the luminescent performance of the natural mineral is greatly restricted by components and structures of the natural mineral, so the luminescent performance is generally poor. However, the material can be artificially synthesized to control the raw material, so that a mineral luminescent material with excellent performance can be obtained, and the material is widely applied to Light Emitting Diodes (LEDs), such as apatite type, pyroxene type, whitlockite type, yttrium aluminum garnet type luminescent materials, and the like. The mineral materials are widely used for White Light Emitting Diodes (WLEDs) such as apatite type, pyroxene type, limonite type and yttrium aluminum garnet type luminescent materials. Yellow light-emitting aluminate phosphor Y based on mineral prototypes3Al5O12：Ce3+Have been commercialized in WLED devices. Unfortunately, modern commercial phosphors still suffer from several recognized problems. For example, for a commercial combination of blue-colored and yellow-emitting phosphors, the absence of a red component in the emission spectrum may result in a lower color rendering index (Ra)<75) Higher color temperature (CCT)>4500K) Energy loss (>20%), color re-absorption and blue light hazards that may damage the retina and brain. These unacceptable fatal drawbacks indicate that red phosphor, an important component of WLED, still leaves much room for improvement to achieve healthy, efficient illumination levels. Much of the previous work has explored the use of red phosphors to improve the illumination quality of WLEDs. It includes the most widely used red nitride phosphor, CaAlSiN3：Eu2+And Sr2Si5N8：Eu2+. Although these phosphors achieve high quantum yields (IQE), the harsh synthesis conditions (high temperature and pressure) and deep red emission limit their large scale application in warm white light production. Moreover, spectral overlap is still an insurmountable threshold. Up to now, red-emitting Mn due to high IQE in blue4+Doped fluoride phosphors have attracted a great deal of attention. However, they also have two serious drawbacks: low Thermal Stability (TS) and use of large amounts of HFAnd (4) acid. Therefore, the development of high-quality red phosphor is still a challenge, and the design is needed.
In addition, no doubt, information security, health care and illumination display are the first major matters of the current society, and exploring how to apply the theoretical research of the fluorescent powder to the application of the fluorescent powder is the most critical innovation direction in the future. However, the research on the development of multifunctional application programs is still deficient at present, but some inventions have made fluorescent powder into anti-counterfeiting ink for anti-counterfeiting printing, but the excitation range of the anti-counterfeiting ink covers the visible light region or the ultraviolet excitation range is wider, so that the anti-counterfeiting and information security protection effects cannot be well embodied. Therefore, if the fluorescent powder with good chemical stability and color stability developed by the patent is made into anti-counterfeiting ink and is applied to printing anti-counterfeiting patterns and encrypted information, the excitation only at specific wavelengths (short-wave ultraviolet light and near ultraviolet light) can be realized. In particular, the current COVID-19 is subject to rapid information security technology in combination with phosphor anti-counterfeiting inks, which makes the health status and audit trails more stringent and rapid.
Disclosure of Invention
The invention provides a preparation method and application of high-stability multifunctional whitlockite fluorescent powder.
The invention comprises the following steps:
the chemical formula of the high-stability multifunctional whitlockite fluorescent powder is (Ca)0.5Sr0.5)3-yM0.07(PO4)2:0.07Ce3+,yMn2+Y is 0,0.01,0.03,0.05,0.07,0.09,0.11, and M is an alkali metal.
Further, the alkali metal is one or more of Li, Na and K.
Further, the present invention comprises the steps of: in the matrix material beta-Ca3(PO4)2Adding sodium ion-containing compound (0.07mol) and Sr cation-containing compound SrCO3According to Ca2+:Sr2+The mol ratio is 1:1, and the high-stability multifunctional whitlockite is obtained by high-temperature solid phase synthesisA fluorescent powder.
Further, CaCO3、SrCO3、(NH4)2HPO4、Na2CO3、CeO2And MnCO3Preheating at 850 deg.C for 1h, and releasing NH in a muffle furnace in air3、H2O and CO2. After regrinding, at 5% H2、55％N2Is placed in a tube furnace and sintered for 10 hours at 1250 ℃. Slowly cooling to room temperature, and grinding into fine powder to obtain the high-stability multifunctional whitlockite type fluorescent powder.
Further, the compound containing sodium ions is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the compound containing Sr cation is one or more of strontium hydroxide, strontium carbonate or strontium bicarbonate.
Further, the high-stability multifunctional whitlockite type fluorescent powder is excited by one or more of ultraviolet light and near ultraviolet light to obtain the high-stability multifunctional whitlockite type fluorescent powder.
An application of high-stability multifunctional whitlockite fluorescent powder in anti-counterfeiting marks,
the invention has the beneficial effects that:
the invention has good thermal stability and chemical stability, realizes the spectrum excitation color development of 550-720nm red light and 720-900nm near-infrared light, can be tuned to red from purple, and has potential application prospect in near-infrared application and field emission display.
Drawings
Fig. 1 shows CNP with standard PDF cards according to the present invention: an XRD spectrum diagram of the Ce, yMn fluorescent powder;
fig. 2 shows a CNP of the present invention: a spectrum schematic diagram of a high-temperature XRD (X-ray diffraction) spectrum of Ce, 0.07Mn fluorescent powder at 25 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 400 ℃, 600 ℃, 800 ℃ and 1000 ℃;
fig. 3 shows a CNP of the present invention: excitation (PL) and emission (PLE) spectra of Ce, 0.07Mn phosphor,
fig. 4 shows a CNP of the present invention: a CIE chromaticity coordinate diagram of Ce, 0.07Mn fluorescent powder, a tuning spectrum diagram of multifunctional whitlockite fluorescent powder with the color from purple to high stability;
fig. 5 shows a CNP of the present invention: ce, yMn (y ═ 0.07) phosphor shows decay profile at continuous I ═ 80mA, Va ═ 8 kV.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
As shown in fig. 1, the present embodiment includes the following steps:
in this example, CaCO was used as the raw material3(≥99.9％)、SrCO3(≥99.9％)、(NH4)2HPO4(≥99.9％)、Na2CO3(99.9％)、CeO2(≧ 99.99%) and MnCO3(99.99%) in the matrix material beta-Ca3(PO4)2Adding a compound containing sodium ions (0.07mol) and a compound containing Sr cations according to Ca2+:Sr2+The mixture is weighed according to the stoichiometric ratio and mixed in an agate mortar, and the mixture is thoroughly ground for 30 minutes. Placing the mixture in a corundum crucible, preheating at 850 deg.C for 1h, and releasing NH in a muffle furnace in air3、H2O and CO2. After regrinding, at 5% H2、55％N2Is placed in a tube furnace and sintered for 10 hours at 1250 ℃. After slowly cooling to room temperature, the product was ground into a fine powder for subsequent characterization.
Fig. 1 CNP with standard PDF cards attached: an XRD (X-ray diffraction) spectrum of the Ce, yMn fluorescent powder proves that the fluorescent powder is a single-phase whitlockite type mineral.
The fluorescent powder has good chemical stability and thermal stability, CL maintains 86.19 percent and 82.30 percent of initial strength after continuous electron radiation for 60min and 90min, and the fluorescent powder has potential application prospects in near infrared and FED. More importantly, the patent also combines a screen printing process to realize two application strategies of a dynamic two-dimensional code for epidemic prevention and an anti-counterfeiting pattern excited by near ultraviolet, which are combined with an information security technology.
In the synthesis and preparation of the fluorescent powder, the CNP: the XRD pattern of Ce, yMn, all well matched to the parent phase beta-Ca3(PO4)2(R3c), Powder Diffraction File (PDF) card number No. 09-0169, indicating that the synthesized sample was a single phase. Good thermal stability is a prerequisite for fluorescent powders to explore CNP: whether the structure of the Ce, yMn fluorescent powder is still stable under high temperature condition or not is determined by selecting CNP: ce, 0.07Mn, XRD patterns were recorded using high temperature X-ray diffraction techniques. Even if the temperature rises to 1000 degrees celsius, CNP: the single phase of the Ce, yMn phosphor did not change, but the position of the diffraction peak was slightly shifted to a small angle, further demonstrating that the stability of the phosphor structure may be responsible for good thermal stability. In addition, the fluorescent powder is tried to be dissolved in common aqueous solution, weak acid and organic solution such as DM, acetone and the like, the fluorescent powder cannot be dissolved in the solution, and the solution is filtered and tested for XPS, so that the signal of elements in the fluorescent powder cannot be detected, and the obtained fluorescent powder is proved to be capable of effectively resisting the corrosion of the weak acid and the organic solution and has good chemical stability.
CNP: the emission spectrum (PL) of a Ce, yMn sample under the excitation of near ultraviolet light 310nm is in two-peak broadband emission, the main peaks are 366nm and 636nm, wherein, the 366nm emission peak is from a Ce3+ center, and the energy transfer of the Ce3+ center enhances the 636nm orange-red emission of Mn2 +. The concentration of Ce3+ ions was fixed at 0.07, and as the concentration of Mn2+ was increased (y was 0,0.01,0.03,0.07,0.11), the intensity of the emission peak centered at 366nm gradually decreased, and the intensity of the emission peak centered at 636nm increased in order, and the color of the phosphor gradually changed from blue to red. But CNP when y is 0.11: ce, yMn concentration quenching occurred at 636nm peak intensity.
As shown in fig. 2, CNP: the high-temperature XRD pattern of Ce, 0.07Mn fluorescent powder at 25 deg.C, 50 deg.C, 100 deg.C, 150 deg.C, 200 deg.C, 400 deg.C, 600 deg.C, 800 deg.C and 1000 deg.C shows that the fluorescent powder has good thermal stability.
The experimental facts prove that the excitation energy can be effectively transferred to Mn2+ ions after being absorbed by Ce3+, and an energy transfer process exists between Ce3+ and Mn2 +. In addition, CNP was found preliminarily: ce, yMn has a near-infrared emission peak at 720nm-890nm, suggesting potential multifunctional applications in near-infrared near-LED bio-penetration, imaging, thermometry, and sensing.
As shown in fig. 3, CNP: the excitation (PL) and emission (PLE) spectra of the Ce, 0.07Mn phosphor showed the emission of 310-500nm near ultraviolet-blue violet light, 550-720nm red light, and 720-900nm near infrared light. SEM (scanning Electron microscope) and corresponding CL (electroluminescent Spectroscopy) mapping images show that the samples exhibit uniform emission, confirming that Ce3+、Mn2+The ions are uniformly distributed in the sample. As the probe current and acceleration voltage increased, the CL intensity gradually increased and no saturation effect was found, indicating that it was more effective for the application of FEDs. Compared with PL, the spectrum shape and the peak position have no obvious change, and two broadband points are shown at 370nm and 620nm and belong to Ce respectively3+And Mn2+The transmission band of light. The intensity of the two CL peaks is gradually reduced along with the increase of the bombardment time, the initial intensity is respectively maintained at 86.19 percent and 82.63 percent after continuous electron irradiation for 60min, and the initial intensity is respectively maintained at 82.30 percent and 81.61 percent after 90min, which are respectively superior to that of the commercial red phosphor Y2O3：Eu3+And Y2O2S：0.05Eu3+Under the same conditions, only 83 percent and 80 percent of strength values are remained, and the good ageing resistance is realized. In summary, experiments at appropriate times (90min) showed that CNP: the Ce, yMn fluorescent powder has good stability in CL strength under the bombardment of low-voltage electron beams, and shows potential advantages in FED application.
As shown in fig. 4, CNP: the color of the Ce, 0.07Mn fluorescent powder realizes the tuning of the multifunctional whitlockite fluorescent powder from purple to high stability in a CIE chromaticity coordinate diagram. Mixing fluorescent powder and Polyvinyl Chloride (PVC) to prepare luminous ink, and printing a two-dimensional code and a school badge on the low-fluorescence paperboard by adopting a screen printing technology. Under the irradiation of natural light, the two-dimensional code and the pattern are not displayed and cannot be read; under the irradiation of ultraviolet light, patterns from purple to red and two-dimensional codes can be easily read. More noteworthy, the two-dimensional code can be read by a Quick Response (QR) scanning application program of the mobile phone, which includes information such as name, department, personal ID, health status, communication permission, and the like, only a simple light source or a flashlight equipped with an ultraviolet lamp is needed, or an ultraviolet lamp device can be added to the identifier, and the information reading is started during the identification. In addition, once the two-dimension code is generated without replacement, the real-time health state can be updated and the passing permission can be set in the background by utilizing the information communication technology, so that the dynamic epidemic prevention is realized. In addition, the use of a non-fluorescent base in actual production produces better results. In summary, with CNP: the anti-counterfeiting pattern made by Ce, yMn has important application prospect in the ultraviolet fluorescence anti-counterfeiting aspect of important documents such as traditional trademarks, certificates, currency and the like, and also provides a new strategy or can effectively realize dynamic epidemic prevention.
To sum up, this patent uses CNP: the anti-counterfeiting pattern made by Ce, yMn has important application prospect in the ultraviolet fluorescence anti-counterfeiting aspect of important documents such as traditional trademarks, certificates, currency and the like, and also provides a new strategy or can effectively realize dynamic epidemic prevention.
As shown in fig. 5, CNP: the decay behavior of the Ce, yMn (y is 0.07) fluorescent powder under continuous I is 80mA, Va is 8kV, the initial intensity of 86.19 percent and 82.63 percent is respectively maintained after 60min of continuous electron irradiation, and the initial intensity of 82.30 percent and 81.61 percent are respectively maintained after 90min, which shows that the fluorescent powder has good stability in CL intensity under low-voltage electron beam bombardment and shows potential advantages in FED application.
The fluorescent powder which has good chemical stability and can be effectively excited by specific wavelength is made into anti-counterfeiting ink, and then the screen printing technology is adopted for making luminous anti-counterfeiting patterns, or the two-dimensional code is made by combining the rapid information security technology and is printed on the passing permission certificate or card, so that the good effect can be obtained in the practical application of information protection, and the health state inquiry and the verification permission become stricter and quicker.
The patent provides a synthesis preparation method of high-stability multifunctional mineral fluorescent powder, which has good thermal stability and chemical stability, can be tuned to red from purple, and has potential application prospects in near-infrared application and field emission display. The fluorescent powder is prepared into anti-counterfeiting ink, and two practical applications are realized through a screen printing technology: (1) the dynamic two-dimensional code is combined with an information security technology and used for epidemic prevention; (2) anti-counterfeiting pattern excited by near ultraviolet. Under the irradiation of natural light, the two-dimensional code and the pattern are not displayed and cannot be read. Under the irradiation of ultraviolet light, patterns from purple to red and two-dimensional codes can be easily read. More noteworthy, the rapid response scanning application program of the mobile phone can read the information including name, department, personal ID, health state, communication permission and the like in the two-dimensional code, only one simple light source or flashlight with an ultraviolet lamp is needed, and ultraviolet lamp equipment can be added into the identifier, and the information reading is started during identification. In addition, once the two-dimension code is generated without replacement, the real-time health state can be updated and the passing permission can be set in the background by utilizing the information communication technology, so that the dynamic epidemic prevention is realized. With CNP: the anti-counterfeiting pattern made by Ce, yMn has important application prospect in the ultraviolet fluorescence anti-counterfeiting aspect of important documents such as traditional trademarks, certificates, currency and the like, and also provides a new strategy or can effectively realize dynamic epidemic prevention.
And programming the target information by using an internet program to generate the two-dimensional code. Manufacturing a screen printing plate (200 meshes) by using the school badge pattern and the two-dimensional code according to a design drawing, and fully mixing fluorescent powder and ss-110 type PVC screen printing ink to prepare fluorescent printing ink, wherein the mass ratio of the powder to the glue is 1: and 2, using a low-fluorescence paperboard as a substrate, placing the screen printing plate above the substrate, uniformly scraping the fluorescent ink with a coating plate, and drying for 10 hours. And placing the obtained card paper under an ultraviolet short-wave light source, and clearly displaying the school badge pattern and the two-dimensional code. The two-dimensional code is scanned by a quick response scanning application program of the mobile phone, so that personal information, health status and passing permission information can be obtained.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. High stabilityThe qualitative multifunctional whitlockite type fluorescent powder is characterized in that the chemical formula of the fluorescent powder is (Ca)0.5Sr0.5)3-yM0.07(PO4)2:0.07Ce3+,yMn2+Y is 0,0.01,0.03,0.05,0.07,0.09,0.11, and M is an alkali metal ion.
2. The highly stable multifunctional whitlockite-type phosphor according to claim 1, wherein the alkali metal is one or more of Li, Na and K.
3. The method for preparing the highly stable multifunctional whitlockite type phosphor according to any one of claims 1 to 2, comprising the steps of: in the matrix material beta-Ca3(PO4)2Adding compound Na containing sodium ion2CO3(0.07mol) and a compound SrCO containing Sr cation3According to Ca2+:Sr2+The high-stability multifunctional whitlockite fluorescent powder is synthesized by a high-temperature solid phase method according to the mol ratio of 1: 1.
4. The method for preparing highly stable multifunctional whitlockite phosphor as claimed in claim 3, wherein CaCO is added3、SrCO3、(NH4)2HPO4、Na2CO3、CeO2And MnCO3Preheating at 850 deg.C for 1h, and releasing NH in a muffle furnace in air3、H2O and CO2(ii) a After regrinding, at 5% H2、55％N2In a reducing atmosphere, placing the mixture in a tubular furnace and sintering the mixture for 10 hours at 1250 ℃; slowly cooling to room temperature, and grinding into fine powder to obtain the high-stability multifunctional whitlockite type fluorescent powder.
5. The method for preparing high-stability multifunctional whitlockite-type phosphor according to claim 3, wherein the compound containing sodium ions is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the compound containing Sr cation is one or more of strontium hydroxide, strontium carbonate or strontium bicarbonate.
6. Use of the highly stable multifunctional whitlockite-type phosphor according to any one of claims 1 to 2, wherein the highly stable multifunctional whitlockite-type phosphor is obtained by exciting the highly stable multifunctional whitlockite-type phosphor according to any one of claims 1 to 2 by one or more of ultraviolet light and near ultraviolet light.
7. An application of high-stability multifunctional whitlockite fluorescent powder in plant growth illumination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110367103.1A CN113061432B (en) | 2021-04-06 | 2021-04-06 | Preparation method and application of high-stability multifunctional whitlockite type fluorescent powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110367103.1A CN113061432B (en) | 2021-04-06 | 2021-04-06 | Preparation method and application of high-stability multifunctional whitlockite type fluorescent powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113061432A true CN113061432A (en) | 2021-07-02 |
| CN113061432B CN113061432B (en) | 2022-06-24 |
Family
ID=76566128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110367103.1A Active CN113061432B (en) | 2021-04-06 | 2021-04-06 | Preparation method and application of high-stability multifunctional whitlockite type fluorescent powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113061432B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113580806A (en) * | 2021-07-21 | 2021-11-02 | 中钞印制技术研究院有限公司 | Security element and security document |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176529A (en) * | 2015-09-19 | 2015-12-23 | 青岛科技大学 | Europium-manganese coactivated phosphate white light fluorescent powder and preparation method thereof |
| CN111978960A (en) * | 2020-07-10 | 2020-11-24 | 贺州学院 | A Synthesis Method of Broadband Excited Phosphate Red Phosphors |
-
2021
- 2021-04-06 CN CN202110367103.1A patent/CN113061432B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176529A (en) * | 2015-09-19 | 2015-12-23 | 青岛科技大学 | Europium-manganese coactivated phosphate white light fluorescent powder and preparation method thereof |
| CN111978960A (en) * | 2020-07-10 | 2020-11-24 | 贺州学院 | A Synthesis Method of Broadband Excited Phosphate Red Phosphors |
Non-Patent Citations (2)
| Title |
|---|
| XIAOFANG YU， XIAOYUN MI: "Color-Tunable Luminescence and Energy Transfer Properties of Dy3+/Eu3+ Co-doped Ca1.5Sr1.5(PO4)2 Phosphor for white LED Applications", 《2020 IEEE 3RD INTERNATIONAL CONFERENCE ON ELECTRONICS TECHNOLOGY (ICET)》 * |
| ZHANG, JC 等: "Near-UV-to-red light conversion through energy transfer in Ca2Sr(PO4)(2):Ce3+,Mn2+ for plant growth", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113580806A (en) * | 2021-07-21 | 2021-11-02 | 中钞印制技术研究院有限公司 | Security element and security document |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113061432B (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rajkumar et al. | Ternary type BaY2ZnO5: Eu3+ deep-red phosphor for possible latent fingerprint, security ink and WLED applications | |
| JP3837588B2 (en) | Phosphors and light emitting devices using phosphors | |
| CN110157424B (en) | A near-infrared phosphor and a light-emitting device containing the phosphor | |
| Shi et al. | Highly efficient and thermally stable CaYMgSbO 6: Mn 4+ double perovskite red phosphor for indoor plant growth | |
| Hussain et al. | Energy transfer mechanism and tunable emissions from K3La (VO4) 2: Dy3+/Eu3+ phosphors and soft-PDMS-based composite films for multifunctional applications | |
| Balakrishnan et al. | Photoluminescence properties and energy transfer in the color tunable Ba2CaZn2Si6O17: Bi3+, Tb3+, Eu3+ silicate phosphor for white LED applications | |
| CN104968763B (en) | Terres rares aluminium garnet type inorganic oxide, fluorophor and employ the light-emitting device of this fluorophor | |
| Guanghuan et al. | Preparation and luminescent properties of CaAl2O4: Eu3+, R+ (R= Li, Na, K) phosphors | |
| Nascimento et al. | Luminescence varied by selective excitation in Eu3+, Tb3+-doped LiSrPO4 phosphors for W-LEDs applications | |
| Balakrishnan et al. | Influence of co-doping alkali metal ions Li+/Na+/K+ on the luminescence enhancement properties of the blue emission from Pb2+/Bi3+ activated di-barium calcium di-zinc hexa-silicate based phosphors for solid state light applications | |
| Qian et al. | Significant enhancement of blue photoluminescence intensity of Dy3+ modified Sr6Ca4 (PO4) 6F2: Eu2+ phosphors | |
| US10619095B2 (en) | NASICON-structured phosphor and light emitting element comprising same luminesent materials | |
| CN107629794A (en) | A kind of europium ion Eu3+The bismuthino luminescent material of activation, preparation method and application | |
| CN104877678A (en) | Yellow long-afterglow luminescent material and preparation method thereof | |
| CN113061432B (en) | Preparation method and application of high-stability multifunctional whitlockite type fluorescent powder | |
| Chung et al. | Ultra-fast synthesis and photoluminescence properties of red-emitting NaBiF4: Eu3+ nanophosphors by various NH4F concentrations | |
| Yu et al. | Tunable blue–green–yellow emitting phosphor of Ba 4 Gd 3 Na 3 (PO 4) 6 F 2: Ce 3+/Tb 3+/Mn 2+ via energy transfer | |
| KR101251609B1 (en) | Yellow Fluorosulfide Phosphors for Light-Emitting Diode And Preparation Method Thereof | |
| Reddy et al. | Enhanced white light emission and energy transfer studies of Dy3+/Ce3+ co-doped YAl3 (BO3) 4 phosphors for white light emitting diodes | |
| Sahu | Studies on the photoluminescence behavior of rare earth (Ce, Sm Eu, Dy, Tb) activated calcium magnesium silicate phosphors | |
| KR100959362B1 (en) | Luminescent material and method of manufacturing the same | |
| Lei et al. | Sol–gel synthesis and photoluminescence properties of a novel Dy 3+ activated CaYAl 3 O 7 phosphor | |
| Yan et al. | Synthesis and photoluminescence properties of Ba1− ySryLa4− xDyx (WO4) 7 (x= 0.04–0.2, y= 0–0.4) phosphors | |
| Chang et al. | Correlating doping with the stability and color rendition of red phosphors | |
| CN104059640B (en) | A kind of borate fluorescent powder substrate and the preparation method of fluorescent material |
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 |