CN112210375A - Rare earth doped silicate fluorescent powder and preparation method thereof - Google Patents
Rare earth doped silicate fluorescent powder and preparation method thereof Download PDFInfo
- Publication number
- CN112210375A CN112210375A CN202011014124.7A CN202011014124A CN112210375A CN 112210375 A CN112210375 A CN 112210375A CN 202011014124 A CN202011014124 A CN 202011014124A CN 112210375 A CN112210375 A CN 112210375A
- Authority
- CN
- China
- Prior art keywords
- fluorescent powder
- rare earth
- temperature
- grinding
- doped silicate
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 39
- 238000000227 grinding Methods 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000007888 film coating Substances 0.000 claims abstract description 16
- 238000009501 film coating Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 14
- 229910018965 MCl2 Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000012717 electrostatic precipitator Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 230000005855 radiation Effects 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 238000010791 quenching Methods 0.000 abstract description 5
- 230000000171 quenching effect Effects 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 4
- -1 rare earth ions Chemical class 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910013885 M3(PO4)2 Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
- C09K11/7796—Phosphates with alkaline earth metals
Abstract
The invention relates to rare earth doped silicate fluorescent powder and a preparation method thereof, wherein the fluorescent powder has the chemical component formula as follows: (M)1‑x，SrX)5(PO4)3‑4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Ca, Ba, Mg or Zn, R is Ce, Dy, Er, Ho or Yb, X is 0.05-0.4, Y is 0.5-2, M is adopted3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Grinding and fully mixing by a high-temperature solid phase method, carrying out primary calcination and secondary calcination, cooling to room temperature, taking out the materials, further crushing and grinding, carrying out ultrasonic cleaning, suction filtration, grinding and drying or further carrying out inorganic film coating treatment by deionized water to obtain a rare earth doped silicate fluorescent powder finished product, and adopting Eu2+As sensitizers, with +3 valent rare earth ions+Excitation broad spectrum overlapping, reduced temperature quenching, overcome weak luminous efficiency and color purity, and emit broad spectrumThe fluorescent powder is wider, the brightness attenuation caused by vacuum ultraviolet radiation and particle bombardment is reduced, the fluorescent brightness and stability are improved, and the plasma display requirement is met.
Description
Technical Field
The invention relates to rare earth doped silicate fluorescent powder and a preparation method thereof, belonging to the technical field of fluorescent powder.
Background
With the rapid development of field emission and plasma light-emitting display technologies, higher requirements are put forward on the performances of the fluorescent powder such as luminous efficiency, granularity, stability, brightness, light decay and the like,the current white light LED comprises yellow fluorescent powder excited by blue light, red, green and blue fluorescent powder excited by purple light or near ultraviolet light, wherein the luminescent material M takes silicate as matrix2SiO4、Sr3SiO5And the like have certain chemical stability and thermal stability, and the raw materials are cheap and easy to obtain, so that the method is widely concerned. The fluorescent powder is doped with a fluorescent inorganic powder material containing rare earth elements, and a high-purity single rare earth compound and other fluorescent-grade chemical raw materials are mixed to prepare the fluorescent powder, so that the fluorescent powder has excellent physical and chemical properties such as photoelectricity or catalysis, and the rare earth tri-color machine fluorescent powder is an ideal energy-saving illumination white light source. However, the rare earth luminescent material in the prior art has the problems that the color purity, the ultraviolet absorption rate, the energy efficiency and the luminous lumen efficiency are difficult to balance, the brightness is attenuated under the vacuum ultraviolet radiation and particle bombardment or the conversion of valence-variable ions, the afterglow time is short, and the requirement of the existing plasma display cannot be met.
Disclosure of Invention
The invention aims to provide rare earth doped silicate fluorescent powder and a preparation method thereof aiming at the defects of the prior art, which can reduce temperature quenching, overcome the defects of weak luminous efficiency and color purity, emit wider broad spectrum, reduce the brightness attenuation caused by vacuum ultraviolet radiation and particle bombardment, improve the fluorescent brightness and stability and meet the display requirements of plasma.
The invention is realized by the following technical scheme:
a rare earth doped silicate fluorescent powder comprises the following chemical components: (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Ca, Ba, Mg or Zn, R is Ce, Dy, Er, Ho or Yb, X is 0.05-0.4, and Y is 0.5-2.
A preparation method of rare earth doped silicate fluorescent powder comprises the following steps:
s1: according to the chemical composition formula (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Ca, Ba, Mg or Zn, R is Ce, Dy, Er, Ho or Yb, X is 0.05-0.4, Y is 0.5-2, and M is weighed according to the calculated proportioning3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Placing in an agate mortar, grinding at room temperature and fully mixing;
s2: placing the ground material in a high-temperature tube furnace, performing high-temperature primary calcination in a reducing atmosphere, wherein the reducing atmosphere is one or more of nitrogen, hydrogen, ammonia, methane, acetylene and propane, the primary calcination temperature is 550-750 ℃, the primary calcination time is 1-3h, and after the material is calcined, taking out the material after the furnace is cooled to room temperature, and further crushing and grinding the material;
s3: placing the material treated by the S2 in a high-temperature tube furnace, and performing high-temperature secondary calcination in a reducing atmosphere, wherein the calcination temperature is 900-1100 ℃, the secondary calcination time is 2-5h, the reducing atmosphere is one or more of nitrogen, hydrogen, ammonia, methane, acetylene and propane, and after the material is cooled to room temperature after calcination, taking out the material for further crushing and grinding;
s4: and (2) performing ultrasonic cleaning, suction filtration, grinding and drying on the material treated by the S3 by using deionized water, wherein the grinding and drying are performed by ball milling treatment and drying, sorting and collection under the traction of hot air of a cyclone separator by a sorting machine, or further performing inorganic film coating treatment, MgO or ZnO is dissolved in an acetic acid solution during the inorganic film coating treatment, the MgO or ZnO is placed in an ultrasonic atomizer and atomized and sprayed into a reaction furnace together with high-pressure carrier gas for film coating treatment of the fluorescent powder at high temperature, the ultrasonic frequency of the ultrasonic atomizer is 100-1000KHz, the wave velocity is 1550m/S, the carrier gas is one or more of oxygen, methane and acetylene, the pressure is 40-60MPa, the temperature of the reaction furnace is 550-650 ℃, and an electrostatic dust collector is used for collecting to obtain the rare earth doped silicate fluorescent powder finished product.
The invention has the beneficial effects that:
(1) by using Eu2+As sensitizers, with +3 valent rare earth ions+Excitation broad spectrum overlap in (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCommon in ClThe doping has stronger coupling effect, reduces temperature quenching, avoids the reduction of optical power and optical effect of a device caused by the rise of temperature during plasma display, ensures that the alkaline earth phosphate silicate has stronger absorption of vacuum ultraviolet, can be effectively excited to generate high-brightness white light by 380-mm long-wave ultraviolet light and blue light, overcomes the defects of weaker luminous efficiency and color purity, has wider emission broad spectrum, and reduces the brightness attenuation caused by vacuum ultraviolet radiation and particle bombardment;
(2) synthesizing rare earth doped silicate fluorescent powder by high temperature solid phase method to make M3(PO4)2And MCl2The fluxing is added, the requirement on reaction temperature is reduced, the preparation process is safe, the flow is simple, the impurity phase is less, the agglomeration is avoided, and the method is suitable for industrial batch production;
(3) the coating rate and compactness are improved by adopting the MgO or ZnO inorganic coating film for ultrasonic spray pyrolysis treatment, so that the uniform and compact coating film has good light transmittance, and the rare earth doped silicate fluorescent powder has higher chemical stability, water resistance and ultraviolet radiation resistance.
Detailed Description
The following examples further illustrate embodiments of the present invention.
Example 1:
a preparation method of rare earth doped silicate fluorescent powder comprises the following steps:
s1: according to the chemical composition formula (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Mg, R is Yb, X is 0.1, Y is 0.6, and M is weighed according to the calculated proportioning3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Placing in an agate mortar, grinding at room temperature and fully mixing;
s2: placing the ground material in a high-temperature tubular furnace, carrying out high-temperature primary calcination in a reducing atmosphere, wherein the reducing atmosphere is nitrogen, the primary calcination temperature is 680 ℃, the primary calcination time is 1.5h, and after calcination, taking out the material after the furnace chamber is cooled to room temperature, and further crushing and grinding the material;
s3: placing the material treated by the S2 in a high-temperature tubular furnace, and performing high-temperature secondary calcination in a reducing atmosphere, wherein the calcination temperature is 975 ℃, the secondary calcination time is 2.5 hours, the reducing atmosphere is nitrogen, and after the material is cooled to room temperature in a hearth after calcination, taking out the material, and further crushing and grinding the material;
s4: and (2) carrying out ultrasonic cleaning, suction filtration and grinding and drying on the material treated by the S3 by using deionized water, wherein the grinding and drying are carried out by ball milling treatment and drying, sorting and collecting by a sorting machine under the traction of hot air of a cyclone separator, or further carrying out inorganic film coating treatment, MgO is dissolved in an acetic acid solution during the inorganic film coating treatment, the MgO is placed in an ultrasonic atomizer and atomized and sprayed into a reaction furnace with high-pressure carrier gas for carrying out film coating treatment on the fluorescent powder at high temperature, the ultrasonic frequency of the ultrasonic atomizer is 500KHz, the wave speed is 1550m/S, the carrier gas is oxygen, the pressure is 50MPa, the temperature of the reaction furnace is 600 ℃, and an electrostatic dust collector is used for collecting and obtaining the rare earth doped silicate fluorescent powder.
Example 2:
a preparation method of rare earth doped silicate fluorescent powder comprises the following steps:
s1: according to the chemical composition formula (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Ba, R is Dy, X is 0.2, Y is 1.2, and M is weighed according to the calculated proportioning3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Placing in an agate mortar, grinding at room temperature and fully mixing;
s2: placing the ground material in a high-temperature tubular furnace, carrying out high-temperature primary calcination in a reducing atmosphere, wherein the reducing atmosphere is propane, the primary calcination temperature is 720 ℃, the primary calcination time is 2.5h, and after calcination, taking out the material after the furnace chamber is cooled to room temperature, and further crushing and grinding the material;
s3: placing the material treated by the S2 in a high-temperature tube furnace, performing high-temperature secondary calcination in a reducing atmosphere, wherein the calcination temperature is 1050 ℃, the secondary calcination time is 4 hours, the reducing atmosphere is propane, and after the material is calcined, taking out the material after the furnace is cooled to room temperature, and further crushing and grinding the material;
s4: and (2) performing ultrasonic cleaning, suction filtration and grinding and drying on the material treated by the S3 by using deionized water, wherein the grinding and drying are performed by ball milling treatment and drying, sorting and collection under the traction of hot air of a cyclone separator by a sorting machine, or further performing inorganic film coating treatment, ZnO is dissolved in an acetic acid solution during the inorganic film coating treatment, the ZnO is placed in an ultrasonic atomizer and atomized and sprayed into a reaction furnace together with high-pressure carrier gas to perform film coating treatment on the fluorescent powder at high temperature, the ultrasonic frequency of the ultrasonic atomizer is 500KHz, the wave speed is 1550m/S, the carrier gas is one or more of oxygen, methane and acetylene, the pressure is 45MPa, the temperature of the reaction furnace is 500 ℃, and an electrostatic dust collector is used for collecting the rare earth doped silicate fluorescent powder finished product.
Example 3:
a preparation method of rare earth doped silicate fluorescent powder comprises the following steps:
s1: according to the chemical composition formula (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Zn, R is Er, X is 0.32, Y is 0.15, and M is weighed according to the calculated metering ratio3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Placing in an agate mortar, grinding at room temperature and fully mixing;
s2: placing the ground material in a high-temperature tubular furnace, carrying out high-temperature primary calcination in a reducing atmosphere, wherein the reducing atmosphere is acetylene, the primary calcination temperature is 570 ℃, the primary calcination time is 3h, and after calcination, taking out the material after the furnace chamber is cooled to room temperature, and further crushing and grinding the material;
s3: placing the material treated in the step S2 in a high-temperature tubular furnace, performing high-temperature secondary calcination in a reducing atmosphere, wherein the calcination temperature is 950 ℃, the secondary calcination time is 3 hours, the reducing atmosphere is methane, and after the material is cooled to room temperature in a hearth after calcination, taking out the material, and further crushing and grinding the material;
s4: and (2) carrying out ultrasonic cleaning, suction filtration and grinding and drying on the material treated by the S3 by using deionized water, carrying out ball milling treatment on the material, drying, sorting and collecting the material under the traction of hot air of a cyclone separator by using a sorting machine, or further carrying out inorganic film coating treatment, dissolving ZnO in an acetic acid solution during the inorganic film coating treatment, placing the material in an ultrasonic atomizer, atomizing and spraying the material and high-pressure carrier gas into a reaction furnace for carrying out film coating treatment on the fluorescent powder at high temperature, wherein the ultrasonic frequency of the ultrasonic atomizer is 800KHz, the wave speed is 1550m/S, the carrier gas is one or more of oxygen, methane and acetylene, the pressure is 45MPa, the temperature of the reaction furnace is 630 ℃, and collecting the material by using an electrostatic precipitator to obtain a rare earth doped silicate fluorescent powder finished.
The mechanism of the invention is as follows:
according to the chemical composition formula (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+M is Ca, Ba, Mg or Zn, R is Ce, Dy, Er, Ho or Yb, and M is3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Grinding and mixing thoroughly, using Eu2+As a sensitizer, electron spins are parallel to each other through a 4f half-filled shell layer, and the + 3-valent rare earth ions have the characteristic of f-f transition and high emission broad spectrum color purity, and unpaired electrons in a 4f orbit can be transited to be used as activated particles of fluorescent powder and are connected with Eu2+Excitation broad spectrum overlap, Eu2+，R3+In (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yThe common doping in Cl has stronger coupling effect, so that the light shape is reduced along with the temperature change, the temperature quenching is reduced, the reduction of the optical power and the optical effect of the device caused by the temperature rise during the plasma display is avoided, the light attenuation is reduced, the lumen efficiency is improved, and the high-brightness white light can be effectively excited by 380 mm long-wave ultraviolet light and blue light;
synthesizing rare earth doped silicate fluorescent powder by a high-temperature solid-phase method, and performing primary calcination and secondary calcination to obtain M3(PO4)2And MCl2The fluxing is added, the melting temperature of other substances is reduced, the reaction temperature requirement is reduced, the luminous intensity of the fluorescent powder is improved, the problem that the luminous performance is influenced due to the fact that the agglomeration hardness of a calcined product is difficult to crush and grind is avoided, and a small amount of reducing atmosphere nitrogen, hydrogen, ammonia, methane, acetylene and propane are filled in the calcined product, so that the preparation process is safe, the flow is simple, and the method is suitable for industrial batch production;
the method comprises the following steps of carrying out calcination and grinding treatment twice, carrying out ultrasonic cleaning, suction filtration, grinding and drying treatment to enable a luminescent crystal center to reach an optimal state, reducing temperature quenching, carrying out ball milling treatment for grinding and drying, carrying out drying, sorting and collecting by a sorting machine under the traction of hot air of a cyclone separator, accelerating production efficiency, controlling the granularity of fluorescent powder to be fine and few impurity phases, and avoiding agglomeration, thereby improving the luminescent brightness;
dissolving MgO or ZnO in acetic acid solution during inorganic film coating treatment, placing the solution in an ultrasonic atomizer, atomizing and spraying the solution and high-pressure carrier gas into a reaction furnace for film coating treatment of the fluorescent powder at high temperature, collecting the solution by using an electrostatic dust collector, obtaining a finished product of the rare earth doped silicate fluorescent powder with the inorganic coated surface by ultrasonic spray pyrolysis, and being beneficial to improving the coating rate and compactness under the condition of proper heat treatment, enabling the uniform and compact coating film to have good light transmittance, endowing the rare earth doped silicate fluorescent powder with higher chemical stability, water resistance and ultraviolet radiation resistance, and avoiding Eu (Eu) from being used for the coating treatment2+The high-temperature oxidation reactor increases oxidation valence at high temperature, reduces thermal stability, resists deliquescence and avoids plasma display chronic corrosion.
Testing and analyzing: and (3) carrying out X-ray diffraction analysis on the synthesized sample by a TD-3000 XRD analyzer, wherein the tube pressure is 30KV tube flow: 20mA, (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+The excitation spectrum has two peaks which are respectively positioned in the ranges of 280-360nm and 450-540 nm;
M1-x/SrXthe ratio of (A) has the influence that the lattice parameter is reduced and the corresponding crystal field intensity is increased with the increase of X, and the excitation broad spectrum moves and expands in the long wave direction with the increase of the radius of the alkaline earth particlesControlling X to be 0.05-0.4, fluorescent powder with better color purity can be obtained, (PO)4)3-4/3y/(SiO4)yHas a strong crystal field, controls Y to be 0.5-2, and the ratio is reduced along with the reduction of Y, Eu2+The mirror body field energy level excited to the 5d state is lower than 4f, has relatively lower characteristic absorption band and has activation, so that the alkaline earth phosphate silicate has stronger absorption in vacuum ultraviolet, overcomes the defects of weaker luminous efficiency and color purity, widens the emission broad spectrum, and reduces the brightness attenuation caused by vacuum ultraviolet radiation and particle bombardment.
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 changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The rare earth doped silicate fluorescent powder is characterized in that the chemical component formula of the fluorescent powder is as follows: (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Ca, Ba, Mg or Zn, and R is Ce, Dy, Er, Ho or Yb.
2. The rare earth-doped silicate phosphor of claim 1, wherein X is 0.05-0.4.
3. The rare earth-doped silicate phosphor of claim 1, wherein Y is 0.5-2.
4. A preparation method of rare earth doped silicate fluorescent powder is characterized by comprising the following steps:
s1: according to the chemical composition formula (M)1-x，SrX)5(PO4)3-4/3y(SiO4)yCl：Eu2+，R3+Wherein M is Ca, Ba, Mg or Zn, R is Ce, Dy, Er, Ho or Yb, and M is weighed according to the calculated and measured proportion3(PO4)2、SrCO3、MCl2、SiO2、Eu2O3、R2O3Placing in an agate mortar, grinding at room temperature and fully mixing;
s2: placing the ground material in a high-temperature tubular furnace, carrying out high-temperature primary calcination in a reducing atmosphere, cooling the material in a hearth to room temperature after calcination, taking out the material, and further crushing and grinding the material;
s3: placing the material treated in the step S2 in a high-temperature tubular furnace, performing high-temperature secondary calcination in a reducing atmosphere, cooling the material in a hearth to room temperature after calcination, taking out the material, and further crushing and grinding the material;
s4: and (3) carrying out ultrasonic cleaning, suction filtration, grinding and drying on the material treated by the S3 with deionized water or further carrying out inorganic film coating treatment to obtain the rare earth doped silicate fluorescent powder.
5. The method according to claim 4, wherein X is 0.05-0.4 and Y is 0.5-2 in step S1, and the reducing atmosphere in steps S2 and S3 is one or more of nitrogen, hydrogen, ammonia, methane, acetylene, and propane.
6. The method as claimed in claim 4, wherein the step S2 is carried out at 550-750 ℃ for 1-3h, the step S3 is carried out at 900-1100 ℃ for 2-5 h.
7. The method according to claim 4, wherein the step S4 is carried out by ball milling, drying with hot air from a cyclone separator, sorting, and collecting.
8. The method according to claim 4, wherein in the step S4, MgO or ZnO is dissolved in acetic acid solution during the inorganic coating treatment, the solution is placed in an ultrasonic atomizer and atomized with high-pressure carrier gas and sprayed into a reaction furnace to carry out coating treatment on the fluorescent powder at high temperature, and an electrostatic precipitator is used to collect the fluorescent powder to obtain the finished product of the rare earth doped silicate fluorescent powder.
9. The method as claimed in claim 8, wherein the ultrasonic frequency of the ultrasonic atomizer is 100-1000KHz, the wave velocity is 1550m/s, the carrier gas is one or more of oxygen, methane and acetylene, the pressure is 40-60MPa, and the temperature of the reaction furnace is 550-650 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011014124.7A CN112210375A (en) | 2020-09-24 | 2020-09-24 | Rare earth doped silicate fluorescent powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011014124.7A CN112210375A (en) | 2020-09-24 | 2020-09-24 | Rare earth doped silicate fluorescent powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112210375A true CN112210375A (en) | 2021-01-12 |
Family
ID=74051850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011014124.7A Pending CN112210375A (en) | 2020-09-24 | 2020-09-24 | Rare earth doped silicate fluorescent powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112210375A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140346A (en) * | 2010-01-29 | 2011-08-03 | 大连路明发光科技股份有限公司 | Eu<2+> activated wlkeite luminescent material and preparation method thereof |
| CN103059849A (en) * | 2013-01-23 | 2013-04-24 | 苏州大学 | Silicophosphate green fluorescent powder activated by Eu<2+> and preparation method as well as application thereof |
| CN105131953A (en) * | 2015-09-09 | 2015-12-09 | 太原理工大学 | Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder |
| CN110028964A (en) * | 2019-04-15 | 2019-07-19 | 杭州电子科技大学 | A kind of white light LEDs apatite structure blue light fluorescent powder and the preparation method of dysprosium-silicon synergy |
-
2020
- 2020-09-24 CN CN202011014124.7A patent/CN112210375A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140346A (en) * | 2010-01-29 | 2011-08-03 | 大连路明发光科技股份有限公司 | Eu<2+> activated wlkeite luminescent material and preparation method thereof |
| CN103059849A (en) * | 2013-01-23 | 2013-04-24 | 苏州大学 | Silicophosphate green fluorescent powder activated by Eu<2+> and preparation method as well as application thereof |
| CN105131953A (en) * | 2015-09-09 | 2015-12-09 | 太原理工大学 | Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder |
| CN110028964A (en) * | 2019-04-15 | 2019-07-19 | 杭州电子科技大学 | A kind of white light LEDs apatite structure blue light fluorescent powder and the preparation method of dysprosium-silicon synergy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2012167517A1 (en) | Method for preparing nitride/oxynitride fluorescent powder used by white led | |
| CN102559179A (en) | Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof | |
| CN110028964B (en) | Dysprosium-silicon synergistic apatite structure blue-light fluorescent powder for white light LED and preparation method thereof | |
| CN101798510A (en) | Nitride phosphor material and preparation method thereof | |
| KR20030060697A (en) | Green-emitting phosphor for long wavelength ultraviolet and a preparation method thereof | |
| CN102585824A (en) | Coprecipitation-rheological phase preparation method of rare earth-doped yttrium aluminum garnet fluorescent powder | |
| JP5926449B2 (en) | Silicate luminescent material having core-shell structure and manufacturing method thereof | |
| CN103834406A (en) | Fluorescent material crystal and preparation method thereof | |
| CN112210375A (en) | Rare earth doped silicate fluorescent powder and preparation method thereof | |
| CN101921590B (en) | Preparation method of rare earth-doped calcium tungstate phosphor | |
| CN108822842B (en) | Red strontium magnesium phosphate fluorescent material and preparation method and application thereof | |
| CN103113889A (en) | Molybdate red phosphor and preparation method thereof | |
| CN101113009A (en) | Preparation method of rare-earth oxide nano particles | |
| CN112592711B (en) | Far-red light fluorescent powder and preparation and modification methods thereof | |
| CN103351865B (en) | Vanadate red phosphor material and preparation method thereof | |
| CN102492422A (en) | Green emitting phosphor for white-light LEDs and preparation method thereof | |
| CN101760191A (en) | High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof | |
| CN101747892A (en) | Red phosphor powder for white light LED and preparation method thereof | |
| Shimomura et al. | Synthesis of Y (P, V) O4: Eu3+ red phosphor by spray pyrolysis without postheating | |
| CN102942930B (en) | Method for preparing high performance aluminate fluorescent powder by pore structure of aluminum oxide | |
| CN112745840A (en) | Near-infrared silicate germanate long-afterglow luminescent material and preparation method thereof | |
| CN102585808B (en) | Borate fluorescent powder for white-light LED and preparation method of borate fluorescent powder | |
| CN101386784B (en) | Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion | |
| Pan et al. | A novel synthesis of alkaline earth silicate phosphor Sr3MgSi2O8: Eu2+, Dy3+ | |
| CN116376539B (en) | LED green powder and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210112 |