CN110129050A - It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method - Google Patents
It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method Download PDFInfo
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- CN110129050A CN110129050A CN201910506251.XA CN201910506251A CN110129050A CN 110129050 A CN110129050 A CN 110129050A CN 201910506251 A CN201910506251 A CN 201910506251A CN 110129050 A CN110129050 A CN 110129050A
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- 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
Abstract
Single-phase full spectrum fluorescent powder is singly mixed the present invention relates to a kind of, the full spectrum fluorescent powder belongs to Ca9MgNa(PO4)7System.Preparation method includes the following steps: S1: weighing raw material, the molar ratio of each component are as follows: (CaCO3/Eu2O3Mixture): (MgCO3)4·Mg(OH)2·5H2O:Na2CO3:NH4H2PO4=90:2:5:70；Wherein CaCO3/Eu2O3CaCO in mixture3With Eu2O3Molar ratio be (8.95~8.98): (0.01~0.025)；S2: load weighted raw material is ground uniform；S3: the raw material after grinding is sintered to 8~12h at 900~1100 DEG C and obtains presoma；S4: presoma is restored at 600~1000 DEG C as reducing agent using Al powder, obtains full spectrum fluorescent powder.Compared with prior art, the present invention is in individually doping Eu2+In the case where ion, by topochemical reaction, Eu is realized2+The regulation of ionic crystals field, and finally realize Eu2+The full spectral emissions of ion high efficiency.
Description
Technical field
The present invention relates to fluorescent powder preparation fields, singly mix single-phase full spectrum fluorescent powder and preparation side more particularly, to a kind of
Method.
Background technique
Green illumination light source of the LED (Light Emitting Diode) as 21 century latest generation, have it is small in size,
Calorific value is low, power consumption is small, the service life is long, fast response time, environmental protection, can planar package easy exploiting at thin short and small product the advantages that.
Generate white light LEDs at present mainly applies traditional yellow fluorescent powder in blue light GaN base LED chip, this fluorescent powder
Emission spectrum is largely green-yellow light, and red color components are less.The white light LEDs colour rendering index of encapsulation is low, no more than traditional white heat
Lamp and fluorescent lamp, in addition several generation white light modes are such as: " red light chips+green light chip+blue chip ", " UV LED chip+
Blue light fluorescent powder+red light fluorescent powder+green light fluorescent powder ".Also due to colour rendering index is low, emission spectrum has discontinuous, light efficiency not
The problems such as high, develops LED in lighting area and is seriously obstructed.
To break through LED in the bottleneck of lighting area, problem above just must overcome.Firstly, the emission spectrum of fluorescent powder
The sensitivity curve that ultraviolet and infra-red radiation should be free of, meet human eye；Secondly the fluorescent powder of this high-quality should have very high aobvious
Colour index is presented the reality color of object.In summary factor considers, only there is the light close to the full spectrum of daylight to be only most
Good illumination light.How to study to obtain that also just to become LED illumination industry instantly close to the light of the full spectrum of daylight most urgent
Project.
Currently, realizing full spectral emissions in mixed fluorescent powder system, meeting is because of the performance difference between fluorescent powder and mutually
Absorbing the stability for leading to fluorescent powder and light efficiency reduces.Meanwhile ion is co-doped with and realizes full spectral emissions as energy efficiency
Being lost excessively high causes luminous efficiency to reduce.
Summary of the invention
Single-phase full light is singly mixed it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
Compose fluorescent powder and preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
Prepared by a kind of claim 1 singly mixes single-phase full spectrum fluorescent powder, and the full spectrum fluorescent powder is Eu2+Doping
Ca9MgNa(PO4)7Compound, molecular formula Ca9MgNa(PO4)7: Eu2+, wherein Eu2+It is partial instead of Ca9MgNa
(PO4)7In Ca2+, Ca9MgNa(PO4)7: Eu2+It is (CaCO by molar ratio3/Eu2O3Mixture): (MgCO3)4·Mg(OH)2·
5H2O:Na2CO3:NH4H2PO4It calcines and obtains after each component grinding of=90:2:5:70, wherein CaCO3With Eu2O3Molar ratio be
(8.95~8.98): (0.01~0.025).
A kind of preparation method for singly mixing single-phase full spectrum fluorescent powder, comprising the following steps:
S1: raw material, the molar ratio of each component are as follows: (CaCO are weighed3/Eu2O3Mixture): (MgCO3)4·Mg(OH)2·
5H2O:Na2CO3:NH4H2PO4=90:2:5:70；
Wherein CaCO3/Eu2O3CaCO in mixture3With Eu2O3Molar ratio be (8.95~8.98): (0.01~
0.025)；
S2: load weighted raw material is ground uniform；
S3: the raw material after grinding is sintered to 8~12h at 900~1100 DEG C and obtains presoma；
S4: presoma is restored at 600~1000 DEG C as reducing agent using Al powder, obtains full spectrum fluorescent powder.
Further, ethyl alcohol is added before grinding during S2, so that raw material is infiltrated.
Further, ball mill or mortar is used to be ground during S2.
Further, it is calcined in air atmosphere during S3.
Further, it is restored under vacuum during S4.
Further, the time restored during S4 is 4~8h.
Further, Al powder is not contacted with presoma during S4.
Further, the mass ratio of Al powder and presoma is (0.03~1) during S4: 1.
Rare earth material is a kind of universal luminescent material, wherein Eu2+With 4fn-15d1Outer-shell electron configuration, 5d track
It is exposed to outer layer, intensity is higher, and fluorescence lifetime is short, and it is more saturated that the property of this width transmitting can just obtain spectrum full light color
Light source, therefore Eu2+It can be applied to lamp phosphor to shine.
It is because phosphate rare earth luminescent material has wider excitation that phosphate is selected in the present invention as host material
Spectrum can be excited by ultraviolet light, near ultraviolet ray and blue light and emit the light of various colors, be widely used in illumination and display.
Compared with prior art, the invention has the following advantages that
1) in individually doping Eu2+In the case where ion, by topochemical reaction, Eu is realized2+The regulation of ionic crystals field,
And finally realize Eu2+The full spectral emissions of ion high efficiency.
2) select the discontiguous Al reduction reaction of Low Temperature Solid-Phase as reduction means, compared with traditional CO atmosphere reduction,
Reducing agent Al powder does not have to and fluorescent powder contact in this method, will not pollute fluorescent powder, and can lower than 1000 DEG C i.e. 600~
Under 1000 DEG C of relatively lower temp, the reduction and spectrum regulation of fluorescent powder are realized.
Detailed description of the invention
Fig. 1 is the luminescence generated by light map of embodiment 2 in the present invention；
Fig. 2 is Ca in the present invention9MgNa(PO4)7The XRD diagram of system fluorescent powder.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
1) prepared by powder: stoichiometrically weighing CaCO3,(MgCO3)4·Mg(OH)2·5H2O,Na2CO3,
NH4H2PO4,Eu2O3Material powder gross mass is 2g, and each material quality ratio is CaCO3:(MgCO3)4·Mg(OH)2·5H2O:
Na2CO3:NH4H2PO4:Eu2O3=0.9677:0.1046:0.0571:0.8670:0.0038.
2) said mixture is placed in agate mortar and is ground 15 to 20 minutes, after mixing to material, by mixture
It loads into alumina crucible, is sealed with the lid of material of the same race, be put in Muffle furnace, calcine 10h in 1050 DEG C of environment.
3) calcined block mixture is taken out, relays shape of claying into power in agate mortar, according to powder after grinding
The ratio that shape mixture and Al powder mass ratio are 1:0.3, weighs mixture and Al powder respectively.
4) mixture weighed up and Al powder are transferred in different alumina crucibles, it is a according still further to a mixture
The order of Al powder is placed into tube furnace, and carries out vacuum pumping, makes airtight vacuum in pipe.
5) it is arranged 1000 DEG C of heating temperature, keeps the temperature 8h.Up to the system fluorescent powder after product is cooled to room temperature.
6) using the crystal structure of X-ray diffractometer (Ultima IV-185) test fluorescent powder, from obtained sample XRD
Test map can be seen that long-range Al powder also raw sample is consistent with standard card, that is, has synthesized single-phase fluorescent powder and purity is fine.
7) Fluorescence Spectrometer (HITACHI F-7000) is used, tests the spectral property of the system fluorescent powder, the results showed that,
The excitation wavelength of the system fluorescent powder is located at 291nm, and emission spectrum covers the visible light of 400nm~750nm wave band.
Embodiment 2:
1) prepared by powder: stoichiometrically weighing CaCO3,(MgCO3)4·Mg(OH)2·5H2O,Na2CO3,
NH4H2PO4, Eu2O3Material powder gross mass is 2g, and each material quality ratio is CaCO3:(MgCO3)4·Mg(OH)2·5H2O:
Na2CO3:NH4H2PO4:Eu2O3=0.9662:0.1045:0.0570:0.8665:0.0057.
2) said mixture is placed in agate mortar and is ground 15 to 20 minutes, after mixing to material, by mixture
It loads into alumina crucible, is sealed with the lid of material of the same race, be put in Muffle furnace, calcine 10h in 1050 DEG C of environment.
3) calcined block mixture is taken out, relays shape of claying into power in agate mortar, according to powder after grinding
The ratio that shape mixture and Al powder mass ratio are 1:0.3, weighs mixture and Al powder respectively.
4) mixture weighed up and Al powder are transferred in different alumina crucibles, it is a according still further to a mixture
The order of Al powder is placed into tube furnace, and carries out vacuum pumping, makes airtight vacuum in pipe.
5) it is arranged 1000 DEG C of heating temperature, keeps the temperature 8h.Up to the system fluorescent powder after product is cooled to room temperature.
6) using the crystal structure of X-ray diffractometer (Ultima IV-185) test fluorescent powder, from obtained sample XRD
Test map can be seen that long-range Al powder also raw sample is consistent with standard card, that is, has synthesized single-phase fluorescent powder and purity is fine.
7) Fluorescence Spectrometer (HITACHI F-7000) is used, tests the spectral property of the system fluorescent powder, referring to Fig. 1,
The result shows that the excitation wavelength of the system fluorescent powder is located at 291nm, emission spectrum covers the visible of 400nm~750nm wave band
Light.
Embodiment 3:
1) powder preparation stoichiometrically weighs CaCO3,(MgCO3)4·Mg(OH)2·5H2O,Na2CO3,NH4H2PO4,
Eu2O3Material powder gross mass is 2g, and each material quality ratio is CaCO3:(MgCO3)4·Mg(OH)2·5H2O:Na2CO3:
NH4H2PO4:Eu2O3=0.9632:0.1044:0.0570:0.8658:0.0094.
2) said mixture is placed in agate mortar and is ground 15 to 20 minutes, after mixing to material, by mixture
It loads into alumina crucible, is sealed with the lid of material of the same race, be put in Muffle furnace, calcine 10h in 1050 DEG C of environment.It will
Calcined block mixture is taken out, and shape of claying into power in agate mortar is relay, according to pulverulent mixture after grinding and Al
Powder mass ratio is the ratio of 1:0.3, weighs mixture and Al powder respectively.
4) mixture weighed up and Al powder are transferred in different alumina crucibles, it is a according still further to a mixture
The order of Al powder is placed into tube furnace, and carries out vacuum pumping, makes airtight vacuum in pipe.
5) it is arranged 1000 DEG C of heating temperature, keeps the temperature 8h.Up to the system fluorescent powder after product is cooled to room temperature.
6) using the crystal structure of X-ray diffractometer (Ultima IV-185) test fluorescent powder, from obtained sample XRD
Test map can be seen that long-range Al powder also raw sample is consistent with standard card, referring to fig. 2, that is, synthesize single-phase fluorescent powder and pure
Degree is fine.
7) Fluorescence Spectrometer (HITACHI F-7000) is used, tests the spectral property of the system fluorescent powder, the results showed that,
The excitation wavelength of the system fluorescent powder is located at 291nm, and emission spectrum covers the visible light of 400nm~750nm wave band.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. a kind of preparation method described in claim 1 for singly mixing single-phase full spectrum fluorescent powder, which is characterized in that including following step
It is rapid:
S1: raw material, the molar ratio of each component are as follows: (CaCO are weighed3/Eu2O3Mixture): (MgCO3)4·Mg(OH)2·5H2O:
Na2CO3:NH4H2PO4=90:2:5:70；
Wherein CaCO3/Eu2O3CaCO in mixture3With Eu2O3Molar ratio be (8.95~8.98): (0.01~0.025)；
S2: load weighted raw material is ground uniform；
S3: the raw material after grinding is sintered to 8~12h at 900~1100 DEG C and obtains presoma；
S4: presoma is restored at 600~1000 DEG C as reducing agent using Al powder, obtains full spectrum fluorescent powder.
2. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S2
Ethyl alcohol is added before grinding, so that raw material is infiltrated.
3. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S2
It is ground using ball mill or mortar.
4. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S3
It calcines in air atmosphere.
5. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S4
It is restored under vacuum.
6. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S4
The time of reduction is 4~8h.
7. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S4
Al powder is not contacted with presoma.
8. a kind of preparation method of full-spectrum LED fluorescent powder according to claim 1, which is characterized in that during S4
The mass ratio of Al powder and presoma is (0.03~1): 1.
9. prepared by a kind of claim 1 singly mixes single-phase full spectrum fluorescent powder, which is characterized in that the full spectrum fluorescent powder is
Eu2+The Ca of doping9MgNa(PO4)7Compound, molecular formula Ca9MgNa(PO4)7: Eu2+, wherein Eu2+It is partial instead of
Ca9MgNa(PO4)7In Ca2+, Ca9MgNa(PO4)7: Eu2+It is (CaCO by molar ratio3/Eu2O3Mixture): (MgCO3)4·Mg
(OH)2·5H2O:Na2CO3:NH4H2PO4It calcines and obtains after each component grinding of=90:2:5:70, wherein CaCO3With Eu2O3's
Molar ratio is (8.95~8.98): (0.01~0.025).
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| CN201910506251.XA CN110129050A (en) | 2019-06-12 | 2019-06-12 | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method |
| PCT/CN2020/095132 WO2020248973A1 (en) | 2019-06-12 | 2020-06-09 | Single-doped single-phase full-spectrum fluorescent powder and preparation method therefor |
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| CN201910506251.XA CN110129050A (en) | 2019-06-12 | 2019-06-12 | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020248973A1 (en) * | 2019-06-12 | 2020-12-17 | 上海应用技术大学 | Single-doped single-phase full-spectrum fluorescent powder and preparation method therefor |
| CN112094644A (en) * | 2020-09-15 | 2020-12-18 | 上海应用技术大学 | Ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder and preparation and application thereof |
| CN113549454A (en) * | 2021-08-24 | 2021-10-26 | 上海应用技术大学 | Eu (II) ion doped single-phase full-spectrum emission fluorescent powder and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974754A (en) * | 2015-07-01 | 2015-10-14 | 上海应用技术学院 | Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof |
| CN109609128A (en) * | 2018-12-29 | 2019-04-12 | 上海应用技术大学 | A kind of green emitting phosphor and preparation method thereof |
| CN109628084A (en) * | 2018-12-29 | 2019-04-16 | 上海应用技术大学 | A kind of blue colour fluorescent powder and its fast preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129050A (en) * | 2019-06-12 | 2019-08-16 | 上海应用技术大学 | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method |
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- 2019-06-12 CN CN201910506251.XA patent/CN110129050A/en active Pending
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2020
- 2020-06-09 WO PCT/CN2020/095132 patent/WO2020248973A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974754A (en) * | 2015-07-01 | 2015-10-14 | 上海应用技术学院 | Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof |
| CN109609128A (en) * | 2018-12-29 | 2019-04-12 | 上海应用技术大学 | A kind of green emitting phosphor and preparation method thereof |
| CN109628084A (en) * | 2018-12-29 | 2019-04-16 | 上海应用技术大学 | A kind of blue colour fluorescent powder and its fast preparation method |
Non-Patent Citations (1)
| Title |
|---|
| ZHIGUO XIA等: "Identification of the crystallographic sites of Eu2+ in Ca9NaMg(PO4)7: structure and luminescence properties study", 《DALTON TRANS.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020248973A1 (en) * | 2019-06-12 | 2020-12-17 | 上海应用技术大学 | Single-doped single-phase full-spectrum fluorescent powder and preparation method therefor |
| CN112094644A (en) * | 2020-09-15 | 2020-12-18 | 上海应用技术大学 | Ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder and preparation and application thereof |
| CN113549454A (en) * | 2021-08-24 | 2021-10-26 | 上海应用技术大学 | Eu (II) ion doped single-phase full-spectrum emission fluorescent powder and preparation method and application thereof |
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| WO2020248973A1 (en) | 2020-12-17 |
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