CN114989810A - Novel tricolor fluorescent powder based on heavy calcium carbonate and preparation method thereof - Google Patents
Novel tricolor fluorescent powder based on heavy calcium carbonate and preparation method thereof Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 109
- 239000000843 powder Substances 0.000 title claims abstract description 93
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 7
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 7
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 7
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229910001940 europium oxide Inorganic materials 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 150000001785 cerium compounds Chemical class 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 239000000758 substrate Substances 0.000 abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 rare earth activated sulfide Chemical class 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- 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
- C09K11/7716—Chalcogenides
- C09K11/7718—Chalcogenides with alkaline earth metals
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- 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
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7744—Chalcogenides
- C09K11/7746—Chalcogenides with alkaline earth metals
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- 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
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Abstract
The novel three-primary-color fluorescent powder based on heavy calcium carbonate consists of red, green and blue rare earth fluorescent powders, wherein the doped element europium in the red rare earth fluorescent powder is 1-10% of the molar mass of the matrix calcium carbonate, the doped element terbium in the green rare earth fluorescent powder is 1-10% of the molar mass of the matrix calcium carbonate, and the doped element cerium in the blue rare earth fluorescent powder is 1-10% of the molar mass of the matrix calcium carbonate. And provides a preparation method of the novel three-primary-color fluorescent powder based on heavy calcium carbonate. The invention adopts calcium carbonate as the substrate of the fluorescent material, can reduce the use amount of rare earth elements, further reduce the cost, and the prepared fluorescent material has good fluorescence performance and thermal stability, and the preparation method is simple and can realize industrialization.
Description
Technical Field
The invention belongs to the technical field of long afterglow luminescent materials, and particularly relates to novel tricolor fluorescent powder based on heavy calcium carbonate and a preparation method thereof.
Background
The long afterglow material, also called light accumulating material, can continuously emit light for several minutes to several hours after the action of external field force is stopped, and is a photoluminescence material with delayed light-emitting effect. The long-afterglow luminescent material generally consists of a substrate and an activator, wherein the substrate plays an important role in the performance of the long-afterglow luminescent material and is a main component of the long-afterglow luminescent material, and the activator is used as a doping element to mainly form a luminescent center and a trap center. Long-lasting phosphors, according to the type of matrix, have evolved from the first generation of sulfides to today, gradually forming several large systems: (1) a sulfide system; (2) an aluminate system; (3) a silicate system. The first long persistence materials discovered were barium sulfide, and later a series of sulfides such as zinc sulfide were used successively as long persistence materials for the phosphor powders. The rare earth activated sulfide system is characterized by the diversity of the luminescent colors from blue to red, which is incomparable with other long afterglow materials at present. However, since the luminescent properties of the sulfide-based long-afterglow luminescent materials are unstable and the afterglow time is short, rare earth-activated alkaline earth aluminates and silicates are the most widely studied long-afterglow luminescent materials in recent years. At present, aluminate or silicate system compounds are mostly used in the common powder of the long afterglow fluorescent paint in the domestic market, and a batch of enterprises represented by Jiangxi Guangyuan group have more complete research teams and long research and development experience. However, long afterglow materials based on aluminates and silicates face two problems: firstly, the luminescent color of the system is concentrated in a blue-green wave band (mainly in the range of 440-520 nm), the research on the corresponding red and near-infrared long-afterglow luminescent materials is not mature enough, and the specific expression is that the types of the materials are few and the performance is poor. Secondly, the long afterglow material of the system has high luminous efficiency and long afterglow time, but is unstable when meeting water, and has high requirement on the purity of raw materials and high production cost.
The calcium carbonate has the advantages of low price, stable chemical property, easily-controlled particle size and morphology and the like, the natural calcium carbonate generally has three crystal forms of calcite, vaterite and aragonite, the different crystal forms cause different positions substituted by doped ions, so that the luminescence performance has great difference, and the characteristics provide great application space for developing novel three-primary-color fluorescent powder luminescent materials taking calcium carbonate as a substrate.
The fluorescent powder is contacted with the outsideEnvironmental impact, both are particularly prone to agglomeration and are not physico-chemical stable. In order to effectively improve and enhance the physical properties and the luminescence properties of the fluorescent powder, the surface of the fluorescent powder is coated and modified, so that the modified fluorescent powder is more and more widely applied. The surface modification method of the fluorescent powder is to coat a layer of inorganic matter or organic matter on the surface of the fluorescent powder by a physical or chemical method. Common inorganic modifiers are oxides, nitrides and phosphates, e.g. SiO 2 、TiO 2 . Examples of the organic modifier include metal alkoxides and organic polymers. After the surface of the fluorescent powder particles is coated with the film material, on one hand, the fluorescent powder particles are isolated from the external environment, the surface structure of the fluorescent powder particles is improved, the surface defects of the fluorescent powder are effectively reduced, and the luminous performance of the material is improved. On the other hand, the surface coating can also effectively control the surface state, surface charge and other physical properties of the fluorescent powder, and improve the stability and the dispersibility of the fluorescent powder. When the fluorescent powder is sintered at high temperature, calcium carbonate powder is easily decomposed into calcium oxide and deliquesced in air, which changes the crystal field environment of the luminescent center and thus changes the electron transition mechanism. Meanwhile, hydroxyl on the surface of calcium carbonate or decomposed calcium oxide is easy to become a non-radiative recombination center, so that the fluorescence efficiency of the powder is weakened. However, the organic coating layer is often only used in indoor warm and humid environments, and is prone to absorb ultraviolet rays outdoors to be aged, so that the service life of the coating layer is affected. Therefore, the development of the inorganic coating technology of the calcium carbonate powder is beneficial to expanding the application scenes of the calcium carbonate fluorescent powder, such as outdoor traffic road marking, safety signs and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of novel three-primary-color fluorescent powder based on heavy calcium carbonate, the calcium carbonate has the characteristics of low price, stable chemical properties, easy control of particle size and morphology and the like, the calcium carbonate can be used as a substrate of a fluorescent material to reduce the use amount of rare earth elements, so that the cost is reduced, the prepared fluorescent material has good fluorescence performance and thermal stability, and the preparation method is simple and can realize industrialization.
In order to solve the technical problems, the invention provides the following technical scheme:
the novel three-primary-color fluorescent powder based on heavy calcium carbonate consists of red, green and blue rare earth fluorescent powders, wherein the doped element europium in the red rare earth fluorescent powder is 1-10% of the molar mass of the matrix calcium carbonate, the doped element terbium in the green rare earth fluorescent powder is 1-10% of the molar mass of the matrix calcium carbonate, and the doped element cerium in the blue rare earth fluorescent powder is 1-10% of the molar mass of the matrix calcium carbonate.
A process for preparing the heavy calcium carbonate-based fluorescent powder with three primary colours includes such steps as doping the compounds containing europium element, terbium element and cerium element respectively as europium oxide, terbium oxide and cerium oxide 3+ 、Mn 2+ As sensitizer, K + Or Li + Supply of electric charge, K 2 CO 3 Or Li 2 CO 3 Fluxing agents and charge compensation agents.
Further, the phosphor powder density: 3-4g/cm 3 The particle size distribution: 1-100um, excitation wavelength: 200-450nm, light emission wavelength: within the range of 400-1000nm, the light-emitting time is as follows: over 8 hours, temperature tolerance: above 400 ℃.
The surface of the prepared rare earth fluorescent powder is coated with inorganic matters such as aluminum oxide and silicon oxide.
The calcium carbonate powder is sintered in a solid phase in a vacuum plasma atmosphere, and a radio frequency power supply is used for exciting working gas such as argon, carbon dioxide gas and the like in a low-pressure environment to generate a plasma atmosphere to activate the surface of the powder.
The calcium carbonate powder is sintered in a low-temperature solid phase manner, the surface of the powder is activated in a plasma atmosphere, and the sintering temperature is lower than 600 ℃.
Sintering calcium carbonate powder at low temperature in a solid phase in a vacuum plasma atmosphere, exciting working gas in a low-pressure environment by using a radio frequency power supply, generating a plasma atmosphere to activate the surface of the powder, and exciting the frequency by using plasma: 10-20MHZ, vacuum degree less than 1X 10 -3 Pa。
The invention has the beneficial effects that: the preparation method is simple and easy to implement, can effectively improve the yield of the calcium carbonate fluorescent powder, protects the calcium carbonate powder substrate from being damaged, can realize industrialization, simplifies the post-treatment process by introducing plasma as a sintering atmosphere, is environment-friendly and efficient, and has great advantages in large-scale production.
The tricolor long afterglow phosphor prepared by the invention can be combined with organic transparent paint, and is used for coating facilities such as building walls, road surfaces and the like, and night illumination lamp scenes.
Drawings
FIG. 1 is a flow chart of the preparation of phosphor powder by plasma sintering.
FIG. 2 is a schematic diagram of a plasma discharge sintering apparatus, wherein 1 is a shielding gas plasma, 2 is a radio frequency power supply, 3 is doped calcium carbonate powder, 4 is a vacuum pump, and 5 is a heater.
FIG. 3 shows the process of ionizing a powder by passing a pulsed current through it, wherein 1 is plasma bombarding the particle surface, 2 is calcium carbonate particles, 3 is heating the substrate, and 4 is a hot zone.
FIG. 4 is a flow chart of the preparation of titanium dioxide coated on the surface of inorganic substance.
Detailed Description
In order to make the technical scheme and advantages of the invention clearer, the technical scheme of the invention is clearly and completely described below with reference to a product drawing. The embodiments described herein are only a few embodiments of the present invention, and all other embodiments obtained by those skilled in the art without making any creative effort based on the embodiments of the present invention belong to the scope of patent protection of the present invention.
Referring to fig. 1 to 4, a novel three primary colors fluorescent powder based on heavy calcium carbonate is composed of red, green and blue rare earth fluorescent powders, wherein the doped element europium in the red rare earth fluorescent powder is 1 to 10% of the molar mass of the matrix calcium carbonate, the doped element terbium in the green rare earth fluorescent powder is 1 to 10% of the molar mass of the matrix calcium carbonate, and the doped element cerium in the blue rare earth fluorescent powder is 1 to 10% of the molar mass of the matrix calcium carbonate.
A process for preparing the heavy calcium carbonate-based fluorescent powder with three primary colours includes such steps as doping the compounds containing europium element, terbium element and cerium element respectively as europium oxide, terbium oxide and cerium oxide,Bi 3+ 、Mn 2+ as sensitizer, K + Or Li + Supply of electric charge, K 2 CO 3 Or Li 2 CO 3 Fluxing agents and charge compensation agents.
Taking the preparation of red calcium carbonate fluorescent powder as an example: weighing a certain amount of CaCO 3 ，Eu 2 O 3 And Li 2 CO 3 The purity requirement of calcium carbonate and lithium carbonate is AR, the purity requirement of europium oxide is 4N, and the proportion of the calcium carbonate to the lithium carbonate is 100: 1: 3, wherein Eu 3+ As activators, Li 2 CO 3 Bi can be added as a cosolvent and a charge compensator 3+ Or Sm 3+ As a sensitizer, the mixture was put into a planetary ball mill and sufficiently ground for 3 hours.
After the completion of the grinding, the powder was placed in a calcination oven, and pre-treated for 120 minutes with 600 ℃ set as the calcination temperature.
The pretreated powder was put into a planetary ball mill and ground again for 6 hours.
Placing the ground powder in a plasma discharge sintering device shown in FIG. 2, and introducing Ar 2 As protective gas, pulse power is set, argon can be punctured through pulse voltage after the pulse voltage reaches a certain value, generated argon ions bombard the surface of the powder, so that the powder generates self-heating to emit electrons to form plasma, and the temperature is rapidly raised. The active area on the surface of the powder particles forms a hot area, so that the ions migrate at high speed to achieve the effect of high-speed diffusion. The RF frequency used in this example was 12.56MHz and the power used was 200W. The sintering temperature was 600 ℃ and the sintering time was 300 minutes. The sintering method has high heat efficiency, and can realize even heating due to the dispersion distribution of the discharge points, thereby creating conditions for preparing high-quality fluorescent powder.
The obtained fluorescent powder is surface-coated by the process shown in FIG. 4, and the coating material is inorganic, such as Al 2 O 3 ，SiO 2 ，TiO 2 ，MgF 2 And the like, and the moisture resistance and the weather resistance are improved. The coating method used by the invention comprises sol-gel coating, wet process and precipitation method. This example usesAnd heating and stirring a precursor prepared from aluminum nitrate and ammonia water to form alumina sol, and coating the fluorescent powder. FIG. four shows the reaction scheme of the method.
The prepared fluorescent powder has the target powder density: 3-4g/cm 3 The particle size distribution: 1-100um, excitation wavelength: 200-450nm, light emission wavelength: within the range of 400-1000nm, the light-emitting time: over 8 hours, temperature tolerance: above 400 ℃.
The scheme of the embodiment adopts the plasma atmosphere to sinter the calcium carbonate powder at a low temperature in a solid phase manner, so that the decomposition phenomenon of calcium carbonate caused by high temperature is avoided, and the low-temperature sintering is favorable for overcoming the fluorescence quenching phenomenon caused by agglomeration in the conventional powder sintering process. Meanwhile, the fluorescent powder is coated by the inorganic substance of silicon oxide or aluminum oxide, so that the fluorescent powder can inhibit fluorescent quenching caused by aggregation while passivating the surface defects of the fluorescent powder, and the surface of the inorganic substance can protect the inside of the fluorescent powder so that the fluorescent powder can work in the environments of ultraviolet, drying and the like. Compared with the existing preparation method of the tricolor fluorescent powder, the preparation method is simpler and more convenient, has low cost, wider application range and stronger luminous performance.
The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the examples, but rather as being defined by the claims and the equivalents thereof which can occur to those skilled in the art upon consideration of the present inventive concept.
Claims (7)
1. The novel three-primary-color fluorescent powder based on heavy calcium carbonate is characterized by consisting of red, green and blue rare earth fluorescent powders, wherein the doped element europium in the red rare earth fluorescent powder accounts for 1-10% of the molar mass of the matrix calcium carbonate, the doped element terbium in the green rare earth fluorescent powder accounts for 1-10% of the molar mass of the matrix calcium carbonate, and the doped element cerium in the blue rare earth fluorescent powder accounts for 1-10% of the molar mass of the matrix calcium carbonate.
2. The method for preparing the novel tricolor fluorescent powder based on heavy calcium carbonate according to claim 1, wherein the method comprisesThe preparation method comprises doping europium, terbium and cerium compounds respectively as europium oxide, terbium oxide, cerium oxide and Bi 3+ 、Mn 2+ As sensitizer, K + Or Li + Supply of electric charge, K 2 CO 3 Or Li 2 CO 3 A fluxing agent and a charge compensating agent.
3. The method for preparing ground calcium carbonate-based novel tricolor fluorescent powder according to claim 2, wherein the powder density of the fluorescent powder is as follows: 3-4g/cm 3 The particle size distribution: 1-100um, excitation wavelength: 200-450nm, light emission wavelength: within the range of 400-1000nm, the light-emitting time is as follows: over 8 hours, temperature tolerance: above 400 ℃.
4. The method for preparing a novel ground calcium carbonate-based trichromatic phosphor according to claim 2, wherein the surface of the prepared rare earth phosphor is coated with inorganic substances such as alumina and silica.
5. The method for preparing heavy calcium carbonate-based novel tricolor fluorescent powder according to claim 2, wherein calcium carbonate powder is solid-phase sintered by using vacuum plasma atmosphere, and working gas such as argon, carbon dioxide gas and the like is excited in low pressure environment by using radio frequency power supply to generate plasma atmosphere to activate the surface of the powder.
6. The method for preparing heavy calcium carbonate-based novel tricolor fluorescent powder according to claim 2, wherein the calcium carbonate powder is sintered in a low-temperature solid phase, the surface of the powder is activated in a plasma atmosphere, and the sintering temperature is less than 600 ℃.
7. The method for preparing heavy calcium carbonate-based novel tricolor fluorescent powder according to claim 2, wherein the calcium carbonate powder is low-temperature solid-phase sintered in vacuum plasma atmosphere, and the working gas is excited in low-pressure environment by using the radio frequency power supply to generateActivating the powder surface by plasma atmosphere, and the plasma excitation frequency: 10-20MHZ, vacuum degree < 1X 10 -3 Pa。
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| CN115353883A (en) * | 2022-08-17 | 2022-11-18 | 浙江工业大学 | Up-conversion fluorescent powder based on heavy calcium carbonate and preparation method thereof |
| CN115353879A (en) * | 2022-08-17 | 2022-11-18 | 浙江工业大学 | Hydrophobic calcium carbonate up-conversion red fluorescent powder and preparation method thereof |
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| CN115353879A (en) * | 2022-08-17 | 2022-11-18 | 浙江工业大学 | Hydrophobic calcium carbonate up-conversion red fluorescent powder and preparation method thereof |
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