CN115322780A - Red fluorescent powder and preparation method and application thereof - Google Patents
Red fluorescent powder and preparation method and application thereof Download PDFInfo
- Publication number
- CN115322780A CN115322780A CN202211031518.2A CN202211031518A CN115322780A CN 115322780 A CN115322780 A CN 115322780A CN 202211031518 A CN202211031518 A CN 202211031518A CN 115322780 A CN115322780 A CN 115322780A
- Authority
- CN
- China
- Prior art keywords
- fluorescent powder
- raw materials
- red
- red fluorescent
- grinding
- 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 41
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000006184 cosolvent Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 235000021317 phosphate Nutrition 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000002178 europium compounds Chemical class 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 150000003388 sodium compounds Chemical class 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 4
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 239000010439 graphite Substances 0.000 description 24
- 229910002804 graphite Inorganic materials 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 239000011734 sodium Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910052693 Europium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010450 olivine Substances 0.000 description 5
- 229910052609 olivine Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 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 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the technical field of luminescent materials, and discloses red fluorescent powder and a preparation method and application thereof. The chemical general formula of the fluorescent powder is NaMg 1‑x Zn x PO 4 :0.03Eu 2+ (ii) a The method provided by the invention comprises the steps of grinding raw materials, pre-burning, and calcining in a protective atmosphere to obtain the red fluorescent powder. The red fluorescent powder has a wide excitation band, can be effectively excited by near ultraviolet light and blue light, has strong absorption in a wave band of 300-500 nm, emits orange red light with a main peak of 634nm or so, and has high emission intensity. The fluorescent powder is prepared by adopting a traditional high-temperature solid phase method, and has the advantages of simple and easy preparation process, low cost and no pollution.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to red fluorescent powder and a preparation method and application thereof.
Background
White Light Emitting Diodes (WLEDs) have found widespread use in solid state lighting applications in recent years. The most common WLED device is a combination of phosphor material and a blue LED chip, the so-called phosphor-converted WLED (pc-WLED). In particular InGaN-based blue LED chips and blue-excited yellow phosphors (e.g., YAG: ce) 3+ ) Combinations of (a) and (b). These pc-WLED systems can show good brightness effects; however, since YAG is Ce 3+ Phosphors do not emit in the red region and their Color Rendering Index (CRI) is poor, resulting in the human eye being unable to recognize the original color of some objects under such poor light sources. Therefore, blue-excited red-emitting phosphors are very important.
In recent years, experts have found a novel multiphase structure consisting of Eu 2+ Activated olivine NaMgPO 4 :Eu 2+ And (3) fluorescent powder. NaMgPO before the olivine phase (high temperature phase) is found 4 The composition of (a) is present only in the low-temperature phase. Eu (Eu) 2+ Doped low temperature phase NaMgPO 4 Exhibits blue light emission under ultraviolet excitation; in contrast, the olivine type NMP is Eu 2+ The phosphor shows high intensity broad red emission at 628nm under 450nm blue excitation. However, olivine type NMP Eu 2+ The synthesis of the fluorescent powder needs a special technology, namely, the synthesis is carried out by an arc imaging furnace, the cost is high, and the large-scale popularization is difficult.
Based on this, a simple and easily repeated synthetic olivine type NMP Eu is studied 2+ The method of phosphor is very important.
Disclosure of Invention
The invention aims to provide red fluorescent powder and a preparation method and application thereof, and solves the problems of the fluorescent powder provided by the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides red fluorescent powder, and the chemical general formula of the red fluorescent powder is NaMg 1-x Zn x PO 4 :0.03Eu 2+ (ii) a Wherein x is more than 0 and less than or equal to 0.12.
The invention also provides a preparation method of the red fluorescent powder, which comprises the following steps:
(1) According to the chemical formula NaMg 1-x Zn x PO 4 :0.03Eu 2+ Weighing raw materials according to the stoichiometric ratio; wherein the raw materials comprise sodium compounds, magnesium compounds, phosphates, europium compounds and zinc compounds;
(2) Mixing the raw materials with acetone, and then grinding to obtain a mixed raw material;
(3) Pre-burning the mixed raw materials, then calcining the mixed raw materials in a protective atmosphere, and cooling the calcined raw materials in the air after calcining to obtain a calcined product;
(4) And grinding the calcined product to obtain the red fluorescent powder.
Preferably, in the above method for preparing a red phosphor, the time for grinding in step (2) is 10 to 30min.
Preferably, in the above method for preparing red phosphor, before the grinding in step (2), a cosolvent is further added; the cosolvent is boric acid.
Preferably, in the above method for preparing red phosphor, the temperature of the pre-firing in the step (3) is 400 to 420 ℃; the pre-sintering time is 3-5 h.
Preferably, in the above method for preparing red phosphor, the calcination temperature in step (3) is 1100 to 1300 ℃; the calcining time is 2-6 h.
Preferably, in the above method for preparing a red phosphor, the protective atmosphere in step (3) is composed of 90 to 95 vol% of nitrogen and 5 to 10 vol% of hydrogen.
Preferably, in the above method for preparing a red phosphor, the particle size after grinding in step (4) is 1 to 25 μm.
The invention also provides application of the red fluorescent powder in paint, a white light conversion diode of fluorescent powder or anti-counterfeiting.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) The red fluorescent powder has a wide excitation band, can be effectively excited by near ultraviolet light and blue light, has strong absorption in a wave band of 300-500 nm, emits orange red light with a main peak of 634nm or so, and has high emission intensity.
(2) The fluorescent powder is prepared by adopting a traditional high-temperature solid phase method, and has the advantages of simple and easy preparation process, low cost and no pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an XRD pattern of the red phosphor of example 1;
FIG. 2 is the excitation and emission spectra of the red phosphor of example 1;
FIG. 3 is a graph showing the excitation spectra of red phosphors of examples 1 and 3 and comparative example 1;
FIG. 4 shows the emission spectra of the red phosphors of examples 1 and 3 and comparative example 1;
fig. 5 is an XRD pattern of the red phosphor of example 7.
Detailed Description
The invention provides red fluorescent powder, and the chemical general formula of the red fluorescent powder is NaMg 1-x Zn x PO 4 :0.03Eu 2+ (ii) a Wherein x is more than 0 and less than or equal to 0.12.
In the present invention, x in the chemical formula of the red phosphor is preferably 0.02 < x.ltoreq.0.1, more preferably 0.04 < x.ltoreq.0.08, and still more preferably 0.05 < x.ltoreq.0.07.
The invention also provides a preparation method of the red fluorescent powder, which comprises the following steps:
(1) According to the chemical formula NaMg 1-x Zn x PO 4 :0.03Eu 2+ Weighing raw materials according to the stoichiometric ratio; wherein the raw materials comprise sodium compounds, magnesium compounds, phosphates, europium compounds and zinc compounds;
(2) Mixing the raw materials with acetone, and then grinding to obtain a mixed raw material;
(3) Pre-burning the mixed raw materials, then calcining the mixed raw materials in a protective atmosphere, and cooling the calcined raw materials in air after calcining to obtain a calcined product;
(4) And grinding the calcined product to obtain the red fluorescent powder.
In the present invention, the sodium compound in step (1) preferably includes one or more of sodium-containing carbonate, sodium-containing hydroxide, sodium-containing nitrate and sodium-containing phosphate, more preferably one or more of sodium carbonate, sodium nitrate and sodium phosphate, and even more preferably sodium nitrate.
In the invention, the magnesium compound in the step (1) preferably comprises one or more of magnesium carbonate, magnesium hydroxide, magnesium nitrate, magnesium sulfate and magnesium phosphate, more preferably one or more of magnesium hydroxide, basic magnesium carbonate, magnesium sulfate and magnesium nitrate, and more preferably magnesium hydroxide.
In the present invention, the phosphate in the step (1) is preferably a phosphate which can be decomposed at a high temperature while not introducing other ions, and is more preferably monoammonium phosphate.
In the present invention, in the step (1), the europium compound preferably includes one or more of europium oxide, europium-containing carbonate, europium-containing hydroxide, europium-containing nitrate, europium-containing sulfate, and europium-containing phosphate, more preferably one or more of europium oxide, europium carbonate, and europium nitrate, and even more preferably europium oxide.
In the present invention, the zinc compound in step (1) preferably comprises one or more of zinc oxide, zinc-containing carbonate, zinc-containing hydroxide, zinc-containing nitrate, zinc-containing sulfate and zinc-containing phosphate, more preferably one or more of zinc oxide, zinc sulfate, zinc phosphate and zinc carbonate, and still more preferably zinc sulfate.
In the present invention, the time for the polishing in the step (2) is preferably 10 to 30min, more preferably 15 to 25min, and still more preferably 20min.
In the invention, the step (2) further comprises adding a cosolvent before grinding; the cosolvent is preferably boric acid; the mass ratio of the cosolvent to the raw materials is preferably 0.01-0.1: 1, more preferably 0.02 to 0.06:1, more preferably 0.03:1.
in the present invention, the mass-to-volume ratio of the raw material to acetone in the step (2) is preferably 1.5g:10 to 30mL, more preferably 1.5g:15 to 25mL, more preferably 1.5g:20mL.
In the present invention, the temperature of the pre-firing in the step (3) is preferably 400 to 420 ℃, more preferably 405 to 416 ℃, and even more preferably 410 ℃; the time for the calcination is preferably 3 to 5 hours, more preferably 3, 3.5, 4, 4.5 or 5 hours, and still more preferably 4.5 hours.
In the present invention, the temperature of the calcination in the step (3) is preferably 1100 to 1300 ℃, more preferably 1140 to 1260 ℃, and still more preferably 1190 ℃; the time for calcination is preferably 2 to 6 hours, more preferably 3 to 5.5 hours, and still more preferably 3.5 hours.
In the present invention, the protective atmosphere in the step (3) is preferably a reducing atmosphere; the reducing atmosphere preferably consists of 90 to 95 volume percent of nitrogen and 5 to 10 volume percent of hydrogen, more preferably 91 to 94 volume percent of nitrogen and 6 to 9 volume percent of hydrogen, and even more preferably 93 volume percent of nitrogen and 7 volume percent of hydrogen.
In the invention, the pre-burning and the calcining in the step (3) both use a heating furnace; the heating furnace is preferably a single-temperature-zone sliding rail furnace.
In the present invention, the particle size after the grinding in the step (4) is preferably 1 to 25 μm, more preferably 3 to 20 μm, and still more preferably 3 to 15 μm.
The invention also provides application of the red fluorescent powder in paint, a white light conversion diode of fluorescent powder or anti-counterfeiting.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides NaMg 0.95 Zn 0.05 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
(1) According to the chemical formula NaMg 0.95 Zn 0.05 PO 4 :0.03Eu 2+ In a stoichiometric ratio of 0.257g of Na was weighed 2 CO 3 (99.8％)、0.447g Mg 2 (OH) 2 CO 3 (99.9％)、0.575gNH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.0204g ZnO (99.9%) as starting materials;
(2) Mixing the raw materials with acetone according to a mass-volume ratio of 1.5g: grinding for 20min after 20mL of mixture to obtain a mixed raw material;
(3) Putting the mixed raw materials into a graphite crucible, then putting the graphite crucible into a single-temperature-zone sliding rail furnace, presintering the graphite crucible at 400 ℃ for 4 hours, then heating the graphite crucible to 1100 ℃ in a reducing atmosphere (consisting of 95 volume percent of nitrogen and 5 volume percent of hydrogen) to calcine the graphite crucible for 4 hours, moving the heating furnace body away after the calcination is finished, and cooling the graphite crucible in air to obtain a calcined product;
(4) The calcined product was ground to 10 μm to obtain red phosphor.
Example 2
This example provides NaMg 0.98 Zn 0.02 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
(1) According to the chemical formula NaMg 0.98 Zn 0.02 PO 4 :0.03Eu 2+ Weighing 0.257g of Na 2 CO 3 (99.8％)、0.462g Mg 2 (OH) 2 CO 3 (99.9％)、0.575gNH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.0081g ZnO (99.9%) as starting materials;
(2) Mixing the raw materials with acetone according to a mass-volume ratio of 1.5g: grinding for 20min after 20mL of mixture to obtain a mixed raw material;
(3) Putting the mixed raw materials into a graphite crucible, then putting the graphite crucible into a single-temperature-zone sliding rail furnace, presintering the graphite crucible at 400 ℃ for 4 hours, then heating the graphite crucible to 1100 ℃ in a reducing atmosphere (consisting of 95 volume percent of nitrogen and 5 volume percent of hydrogen) to calcine the graphite crucible for 4 hours, moving the heating furnace body away after the calcination is finished, and cooling the graphite crucible in air to obtain a calcined product;
(4) The calcined product was ground to 5 μm to obtain red phosphor.
Example 3
This example provides NaMg 0.97 Zn 0.03 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
(1)according to the chemical formula NaMg 0.97 Zn 0.03 PO 4 :0.03Eu 2+ In a stoichiometric ratio of 0.257g of Na was weighed 2 CO 3 (99.8％)、0.457g Mg 2 (OH) 2 CO 3 (99.9％)、0.575g NH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.0122g ZnO (99.9%) as starting materials;
(2) Mixing the raw materials with acetone according to a mass-volume ratio of 1.5g: grinding for 20min after 20mL of mixture to obtain a mixed raw material;
(3) Putting the mixed raw materials into a graphite crucible, then putting the graphite crucible into a single-temperature-zone sliding rail furnace, presintering the graphite crucible at 400 ℃ for 4 hours, then heating the graphite crucible to 1100 ℃ in a reducing atmosphere (consisting of 95 volume percent of nitrogen and 5 volume percent of hydrogen) to calcine the graphite crucible for 4 hours, moving the heating furnace body away after the calcination is finished, and cooling the graphite crucible in air to obtain a calcined product;
(4) The calcined product was ground to 15 μm to obtain red phosphor.
Example 4
This example provides NaMg 0.96 Zn 0.04 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
(1) According to the chemical formula NaMg 0.96 Zn 0.04 PO 4 :0.03Eu 2+ Weighing 0.257g of Na 2 CO 3 (99.8％)、0.452g Mg 2 (OH) 2 CO 3 (99.9％)、0.575g NH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.0163g ZnO (99.9%) as starting materials;
(2) Mixing the raw materials with acetone according to the mass volume ratio of 1.5g: grinding for 20min after 20mL of mixture to obtain a mixed raw material;
(3) Putting the mixed raw materials into a graphite crucible, then putting the graphite crucible into a single-temperature-zone sliding rail furnace, presintering the graphite crucible at 400 ℃ for 4 hours, then heating the graphite crucible to 1100 ℃ in a reducing atmosphere (consisting of 95 volume percent of nitrogen and 5 volume percent of hydrogen) to calcine the graphite crucible for 4 hours, moving the heating furnace body away after the calcination is finished, and cooling the graphite crucible in air to obtain a calcined product;
(4) And grinding the calcined product to 8 mu m to obtain red fluorescent powder.
Example 5
This example provides NaMg 0.94 Zn 0.06 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
according to the chemical formula NaMg 0.94 Zn 0.06 PO 4 :0.03Eu 2+ In a stoichiometric ratio of 0.257g of Na was weighed 2 CO 3 (99.8％)、0.442g Mg 2 (OH) 2 CO 3 (99.9％)、0.575gNH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.0244g ZnO (99.9%) as starting materials; see example 1 for subsequent preparation.
Example 6
This example provides NaMg 0.93 Zn 0.07 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
according to the chemical formula NaMg 0.93 Zn 0.07 PO 4 :0.03Eu 2+ Weighing 0.257g of Na 2 CO 3 (99.8％)、0.437g Mg 2 (OH) 2 CO 3 (99.9％)、0.575gNH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.0285g ZnO (99.9%) as starting materials; see example 1 for subsequent preparation.
Example 7
This example provides NaMg 0.97 Zn 0.03 PO 4 :0.03Eu 2+ The red phosphor, see example 3 specifically, except that boric acid was also added as a cosolvent in step (2) before grinding (the mass ratio of boric acid to starting material was 0.03.
Example 8
This example provides NaMg 0.98 Zn 0.02 PO 4 :0.03Eu 2+ The red phosphor, see example 2 specifically, except that boric acid was also added as a cosolvent in step (2) before grinding (the mass ratio of boric acid to raw material was 0.03.
Example 9
This example provides NaMg 0.99 Zn 0.01 PO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
according to the chemical formula NaMg 0.99 Zn 0.01 PO 4 :0.03Eu 2+ Weighing 0.257g of Na 2 CO 3 (99.8％)、0.467g Mg 2 (OH) 2 CO 3 (99.9％)、0.575gNH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) and 0.004g ZnO (99.9%) as starting materials; see example 8 for subsequent preparation.
Comparative example 1
This comparative example provides NaMgPO 4 :0.03Eu 2+ The preparation method of the red fluorescent powder comprises the following steps:
according to the chemical formula NaMgPO 4 :0.03Eu 2+ Weighing 0.257g of Na 2 CO 3 (99.8％)、0.472g Mg 2 (OH) 2 CO 3 (99.9％)、0.575gNH 4 H 2 PO 4 (99.0％)、0.0264g Eu 2 O 3 (99.99%) as a starting material; see example 1 for subsequent preparation.
The red phosphor prepared in example 1 was subjected to XRD characterization, and the result is shown in fig. 1. As can be seen from figure 1, the XRD diffraction peak of the red fluorescent powder is well matched with a standard card, and the phase of the material is NaMgPO 4 A high temperature phase.
The red phosphor prepared in example 1 was subjected to excitation and emission spectrum tests, and the results are shown in fig. 2. As can be seen from FIG. 2, the excitation spectrum is a relatively broad absorption spectrum (280 to 540 nm), the peak of the excitation peak is at 374nm, and the emission spectrum shows a broad emission peak at 626 nm.
The red phosphors of examples 1 and 3 and comparative example 1 were subjected to excitation and emission spectrum tests, respectively, and the results are shown in fig. 3 to 4. As can be seen from FIGS. 3 to 4, examples 1 and 3 incorporated Zn in comparison with the excitation and emission spectra of the red phosphor of comparative example 1 2+ The obtained red fluorescent powder has strong emission peakDegree increases and emission peak intensity follows Zn 2+ Increased amount of the doped Zn complex 2+ The strongest is achieved with x =0.05 incorporation.
The red phosphor prepared in example 7 was subjected to XRD characterization, and the result is shown in fig. 5. As can be seen from FIG. 5, the XRD diffraction peak of the red phosphor powder is well matched with the standard card, and the phase of the material is NaMgPO 4 And in the high-temperature phase, the impurity content of the sample obtained after adding the cosolvent boric acid is reduced, and the crystallinity is increased.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The red fluorescent powder is characterized in that the chemical general formula of the red fluorescent powder is NaMg 1-x Zn x PO 4 :0.03Eu 2+ (ii) a Wherein x is more than 0 and less than or equal to 0.12.
2. The method of claim 1, comprising the steps of:
(1) According to the chemical formula NaMg 1-x Zn x PO 4 :0.03Eu 2+ Weighing raw materials according to the stoichiometric ratio; wherein the raw materials comprise sodium compounds, magnesium compounds, phosphates, europium compounds and zinc compounds;
(2) Mixing the raw materials with acetone, and then grinding to obtain a mixed raw material;
(3) Pre-burning the mixed raw materials, then calcining the mixed raw materials in a protective atmosphere, and cooling the calcined raw materials in air after calcining to obtain a calcined product;
(4) And grinding the calcined product to obtain the red fluorescent powder.
3. The method as claimed in claim 2, wherein the grinding time in step (2) is 10-30 min.
4. The method of claim 3, wherein the step (2) of adding a cosolvent before grinding; the cosolvent is boric acid.
5. The method for preparing red phosphor according to claim 2 or 4, wherein the pre-sintering temperature in the step (3) is 400-420 ℃; the pre-sintering time is 3-5 h.
6. The method of claim 5, wherein the calcining temperature in step (3) is 1100-1300 ℃; the calcining time is 2-6 h.
7. The method as claimed in claim 2, 4 or 6, wherein the protective atmosphere in step (3) is composed of 90-95 vol% nitrogen and 5-10 vol% hydrogen.
8. The method of claim 7, wherein the particle size of the red phosphor in step (4) is 1-25 μm.
9. The use of the red phosphor of claim 1 in coatings, phosphor-to-white light diodes, or anti-counterfeiting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211031518.2A CN115322780B (en) | 2022-08-26 | 2022-08-26 | Red fluorescent powder and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211031518.2A CN115322780B (en) | 2022-08-26 | 2022-08-26 | Red fluorescent powder and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115322780A true CN115322780A (en) | 2022-11-11 |
| CN115322780B CN115322780B (en) | 2024-07-23 |
Family
ID=83928794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211031518.2A Active CN115322780B (en) | 2022-08-26 | 2022-08-26 | Red fluorescent powder and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115322780B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014136840A1 (en) * | 2013-03-06 | 2014-09-12 | 国立大学法人 新潟大学 | Phosphate phosphor and method for manufacturing phosphate phosphor |
| CN104870604A (en) * | 2012-12-21 | 2015-08-26 | 默克专利有限公司 | Luminescent substances |
-
2022
- 2022-08-26 CN CN202211031518.2A patent/CN115322780B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104870604A (en) * | 2012-12-21 | 2015-08-26 | 默克专利有限公司 | Luminescent substances |
| WO2014136840A1 (en) * | 2013-03-06 | 2014-09-12 | 国立大学法人 新潟大学 | Phosphate phosphor and method for manufacturing phosphate phosphor |
Non-Patent Citations (2)
| Title |
|---|
| K. TODA, ET AL.: "Blue Light Excitable Red-Emitting Oxide Phosphor", ABSTRACT #2708, 224TH ECS MEETING, © 2013 THE ELECTROCHEMICAL SOCIETY * |
| M. AMER, ET AL.: "The doping sites in Eu2+-doped AIBIIPO4 phosphors and their consequence on the photoluminescence excitation spectra", JOURNAL OF SOLID STATE CHEMISTRY * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115322780B (en) | 2024-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101475497B1 (en) | Aluminum-silicate based orange-red phosphors with mixed divalent and trivalent cations | |
| US9150785B2 (en) | Red fluorescent materials and preparation methods thereof | |
| WO2012088788A1 (en) | Oxynitride luminescent material, preparation method thereof and illumination light source made from such material | |
| KR20070117003A (en) | Phosphor and light emission appliance using phosphor | |
| TW200909564A (en) | Silicate-base luminescent material with muti-emission peak, a method of manufacturing the same and a lighting apparatus using the same | |
| CN112457848B (en) | Narrow-band blue light fluorescent powder and preparation method and application thereof | |
| CN113185977B (en) | Europium-doped ultra-wideband red fluorescent material and preparation method and application thereof | |
| KR101420337B1 (en) | White-light led red luminescent materials and preparation methods thereof | |
| KR20170100412A (en) | Nitroxide fluorescent powder and method for preparing same, nitroxide illuminant, and luminescent device | |
| CN102108297B (en) | Red fluorescent powder, preparation method thereof and luminescent device prepared therefrom | |
| CN115368893A (en) | Sodium gadolinium gallium germanium garnet-based green fluorescent powder and preparation method thereof | |
| CN113201342A (en) | Ce3+Activated silicate broadband green fluorescent powder and preparation method and application thereof | |
| CN109370580B (en) | Bismuth ion activated titanium aluminate fluorescent powder and preparation method and application thereof | |
| CN106147759A (en) | A kind of white light LEDs borate substrate fluorescent powder and preparation method thereof | |
| CN108517210B (en) | Ce3+, Dy3+Doped color-controllable phosphor and method of making same | |
| CN112480924B (en) | Gallate red-light fluorescent material, preparation method thereof and white-light LED light-emitting device | |
| CN103571481A (en) | Molybdate red phosphor for activating europium ion Eu<3+>, and preparation method and application of molybdate red phosphor | |
| CN112625683A (en) | Germanate type red fluorescent powder and preparation method thereof | |
| CN108822842B (en) | Red strontium magnesium phosphate fluorescent material and preparation method and application thereof | |
| CN115287066B (en) | Eu (Eu) 2+ Activated halogen-containing borate green-light fluorescent powder and preparation method and application thereof | |
| CN115322780B (en) | Red fluorescent powder and preparation method and application thereof | |
| EP1849192B1 (en) | White light emitting device | |
| CN110272740B (en) | Zero-doped rare earth borate red fluorescent powder, preparation and application thereof in L ED field | |
| CN113416542A (en) | Red fluorescent powder capable of being excited by blue light and preparation method thereof | |
| Xiaochun et al. | Influences of phase composition on Sr3SiO5: Eu2+ luminous performance |
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 |