CN103173225B - Blue fluosilicate fluorescent powder as well as preparation method and application - Google Patents
Blue fluosilicate fluorescent powder as well as preparation method and application Download PDFInfo
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- CN103173225B CN103173225B CN201310114889.1A CN201310114889A CN103173225B CN 103173225 B CN103173225 B CN 103173225B CN 201310114889 A CN201310114889 A CN 201310114889A CN 103173225 B CN103173225 B CN 103173225B
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- 239000000843 powder Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims description 53
- 239000011575 calcium Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 10
- -1 silicon ion Chemical class 0.000 claims description 9
- 239000011775 sodium fluoride Substances 0.000 claims description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 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 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 238000003836 solid-state method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 44
- 238000000034 method Methods 0.000 abstract description 9
- 230000005284 excitation Effects 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 229910019443 NaSi Inorganic materials 0.000 abstract 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 229940104869 fluorosilicate Drugs 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 6
- 229910004261 CaF 2 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 150000004645 aluminates Chemical group 0.000 description 3
- 238000005516 engineering process Methods 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001753 sapphirine Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
本发明公开了一种氟硅酸盐蓝色荧光粉、制备方法及应用，属无机发光材料技术领域。所述荧光粉的化学式为：Ca2-2xEu2xNaSi4O10F，其中0.0001＜x≤0.25，采用高温固相法制备得到。它在波长为350～420纳米的近紫外光激发下，发射出中心波长在450纳米附近的蓝色荧光，发光强度高、稳定性好；在近紫外光的激发，与近紫外半导体芯片的发射波长非常吻合，可作为近紫外光激发的白光LED用荧光粉。且该荧光粉中的阳离子主要为碱土金属、稀土金属，烧结工艺简单，重现性好，所得产品质量稳定，易于操作和工业化生产。
The invention discloses a fluorosilicate blue fluorescent powder, a preparation method and an application thereof, and belongs to the technical field of inorganic luminescent materials. The chemical formula of the fluorescent powder is: Ca 2-2x Eu 2x NaSi 4 O 10 F, where 0.0001<x≤0.25, and it is prepared by a high-temperature solid phase method. Under the excitation of near-ultraviolet light with a wavelength of 350-420 nanometers, it emits blue fluorescence with a center wavelength near 450 nanometers, with high luminous intensity and good stability; The wavelength is very consistent, and it can be used as a phosphor powder for white LEDs excited by near-ultraviolet light. Moreover, the cations in the fluorescent powder are mainly alkaline earth metals and rare earth metals, the sintering process is simple, the reproducibility is good, the quality of the obtained product is stable, and the operation and industrial production are easy.
Description
Technical field
The present invention relates to a kind of fluorescent material and preparation method thereof, be particularly useful for high-brightness blue silicofluoride fluorescent material of LED and preparation method thereof, belong to rare earth luminescent material technical field.
Background technology
Along with global energy worsening shortages and environmental stress increase day by day, energy-conserving and environment-protective become the current important topic facing, and in general lighting field, white light LEDs product is just attracting increasing concern.White light LEDs is as novel green illuminating product, has that photoelectric efficiency is high, the life-span is long, volume is little, power is low, an advantage such as solid-state energy-conservation and environmental protection, is generally acknowledged novel illumination light source, must become following development trend.21st century is by the novel illumination light source epoch that enter taking LED as representative.Fluorescent material is as the important component part of white light LEDs, has great importance for improving the performance index such as the luminous efficiency, work-ing life, colour temperature, colour rendering index of such LED.
At present, the approach that realizes of White-light LED illumination mainly contains three kinds: the combined and volume subtype of light conversion hysteria, polychrome.Wherein, adopting the light transformation approach of the luminous formation mixed white light of LED excitated fluorescent powder LED is current mainstream technology, and reported luminous efficiency white light LEDs product the highest and that commercially produced is all based on this method.Business-like white light LEDs is that the blue light (approximately 450 nanometer) that Japanese Nichia company uses GaN base LED chip to send carrys out excitation rare-earth fluorescent material YAG (Y the earliest
3al
5o
12): Ce
3+yellow light-emitting low temperature, thus white light formed.But, because of shortcomings such as it lack red light portion radiation, and product exists colour rendering index low, and color reducibility is poor, be restricted in widespread adoption and the popularization of high-end lighting field.The emission wavelength of current I nGaN chip blue shift, near ultraviolet region, can provide higher excitation energy for fluorescent material.The combination of ultraviolet or near ultraviolet LED and three primary colors fluorescent powder, its color developing is best, and fluorescent material luminous efficiency is lower.Therefore development of new redness, green and blue colour fluorescent powder efficient, Heat stability is good is the key that improves white light LEDs luminous mass.
At present, can be used for the blue colour fluorescent powder of near ultraviolet (350～420 nanometer) type white light LEDs (NUV-LED) use also few.Wherein, studying more is aluminate base blue colour fluorescent powder, mainly taking high temperature solid-state method as main.As Chinese invention patent CN1415695A discloses the preparation method of the blue aluminate fluorescent powder that a kind of vacuum ultraviolet rays activates.That the method has is easy and simple to handle, technique simple, low cost and other advantages, but thing is assorted and particle is thick mutually, and pattern is irregular, and follow-up disintegrating process can cause declining to a great extent of light-emitting phosphor performance and use properties; Chinese invention patent CN1190115A discloses BaMgAl
14o
23: the preparation method of Eu blue colour fluorescent powder, this patent is that carbon dust is directly covered on starting material, this preparation method, because carbon dust is directly to contact with starting material, causes fluorescent material part Prevent Carbon Contamination, thereby causes the waste of starting material in preparation process.Therefore, this preparation method can not meet the needs of actual production well.But, silicate has good chemical stability and thermostability as inorganic fluorescent material, raw material is cheap, also be the fluorescence synthetic materials with high-luminous-efficiency simultaneously, and there are higher crystallinity and visible light permeability, it is a kind of better luminescent material, can be applied in preferably in the fluorescent material that near ultraviolet type white light LEDs uses, as Chinese invention patent CN102703066A discloses a kind of silicofluoride fluorescent material and preparation method thereof, this fluorescent material is rare-earth ion activated lithium fluosilicate calcium fluorescent material, and its chemical expression is Ca
2-xliSiO
4f:xR
2+, 0<x<0.1, R
2+for Eu
2+; Or be Ca
2-2xliSiO
4f:x (R
3++ Li
+), 0<x<0.5, R
3+for Eu
3+, Sm
3+, Tb
3+, Dy
3+, Ce
3+in one.The silicate blue fluorescent powder of this invention can be excited by 250～350 nano-ultraviolet lights, sends the blue colour fluorescent powder of efficient main emission peak in 460 nanometer range.But such fluorescent material need to be at H
2+ N
2among reducing atmosphere, synthesize H in building-up process
2+ N
2can not be penetrated into for a full due among synthetic fluorescent material powder Deng reducing gas, make the active ions of fluorescent material can not be reduced to fully Ce
3+, badly influence the luminous of fluorescent material; Also due to H
2+ N
2reducing gas has danger, and misoperation can set off an explosion, and therefore, its production has been subject to certain restriction.
Silicate systems fluorescent material is except the good warm and chemical stability advantage of matrix, also there are raw material sources abundant simultaneously, the advantages such as synthesis technique adaptability is extensive, find the high sapphirine silicate systems fluorescent material effectively being excited near ultraviolet 350-420 nano waveband, be expected to be used in white light LEDs field.
Summary of the invention
The deficiency existing in order to overcome prior art, the object of this invention is to provide one can be excited by ultraviolet leds, there is good luminous characteristic and physical and chemical performance, silicofluoride blue colour fluorescent powder for LED that manufacturing process is simple, pollution-free, cost is low and preparation method thereof, to overcome deficiency of the prior art.
For reaching above object, the technical solution used in the present invention is: a kind of silicofluoride blue colour fluorescent powder is provided, and its chemical formula is Ca
2-2xeu
2xnaSi
4o
10f, wherein 0.0001 < x≤0.25; Be under the ultraviolet excitation of 350～420 nanometers at wavelength, launch the blue-fluorescence that main wavelength is 450～475 nanometers.
Prepare a silicofluoride blue colour fluorescent powder method as above, adopt high temperature solid-state method, comprise the following steps:
(1) to contain calcium ion Ca
2+compound, contain sodium ion Na
+compound, contain silicon ion Si
4+compound, europium ion Eu
3+for raw material, by molecular formula Ca
2-2xeu
2xnaSi
4o
10in F (wherein 0.0001 < x≤0.25), the stoichiometric ratio of corresponding element takes each raw material; The raw material taking is ground respectively, and remix is even, obtains mixture;
(2) other mixtures except fluorochemical are calcined under air atmosphere, calcining temperature is 100～500 DEG C, and calcination time is 1～10 hour;
(3) by the mixture naturally cooling after calcining, grind and mix, sintering (described reducing atmosphere is active carbon granule reducing atmosphere) in the atmosphere of reduction, calcining temperature is 600～1000 DEG C, calcination time is 2～8 hours;
(4) by the mixture naturally cooling after calcining; add fluorochemical to grind and mix; sintering (described reducing atmosphere is active carbon granule reducing atmosphere) in the atmosphere of reduction; calcining temperature is 800～1200 DEG C; calcination time is 2～10 hours, obtains a kind of silicofluoride blue colour fluorescent powder.
When the present invention adopts high temperature solid-state method, the described calcining temperature of step (2) is 300～500 DEG C, and calcination time is 3～8 hours; The described calcining temperature of step (3) is 700～1000 DEG C, and calcination time is 4～7 hours; The described calcining temperature of step (4) is 1000～1200 DEG C, and calcination time is 5～10 hours.
The calcium ion Ca that contains of the present invention
2+compound comprise the one in calcium oxide, calcium carbonate; Contain sodium ion Na
+compound comprise the one in sodium oxide, sodium carbonate; Contain silicon ion Si
4+compound be silicon-dioxide; Contain fluorion F
-compound comprise Calcium Fluoride (Fluorspan) or Calcium Fluoride (Fluorspan) and Sodium Fluoride; The described europium ion Eu that contains
3+compound oxidation europium, europium nitrate in one.
The blue colour fluorescent powder of silicofluoride provided by the invention, is coordinated appropriate redness, green emitting phosphor, applies and is packaged in outside InGaN diode, prepares white light LEDs illuminating device.
Compared with prior art, the advantage of technical solution of the present invention is:
1, the silicofluoride that prepared by the present invention has good chemical stability and thermostability, and raw material is cheap, wide material sources, and cost is lower, is also the fluorescence synthetic materials with high-luminous-efficiency simultaneously, resistance to uv irradiation.
2, the fluorescent material of this invention has very wide excitation spectrum near ultraviolet region (350-420 nanometer), can stick on indium gallium nitride near-ultraviolet light LED chip and obtain efficient blue-light-emitting, coordinate again near ultraviolet excitated redness, green emitting phosphor, can realize white luminous that near-ultraviolet light LED excites, prepare White-light LED illumination device.
3, silicofluoride blue-fluorescence powder preparation technique provided by the invention is simple, easy handling, with the comparison of aluminates system fluorescent material, synthesis temperature low (1000～1200 DEG C), thereby obviously reduce energy consumption and product cost, material preparation for the requirement of equipment well below similar fluorescent material.
4, synthesis material Sodium Fluoride used in the present invention, Calcium Fluoride (Fluorspan) all have the effect of fluxing, and reduce temperature of reaction, improve reactive behavior, have wide application prospect.Product easily collecting simultaneously, without waste water and gas discharge, environmental friendliness, is especially applicable to serialization and produces.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction collection of illustrative plates of the material sample prepared by the embodiment of the present invention 1 technical scheme;
Fig. 2 is the material sample prepared by the embodiment of the present invention 1 technical scheme luminescent spectrum figure under the optical excitation of 395 nanometers;
Fig. 3 is the exciting light spectrogram of the ultraviolet that obtains under the light detection of 450 nanometers of the material sample prepared by the embodiment of the present invention 1 technical scheme to blue region;
Fig. 4 is that the material sample of preparing by the embodiment of the present invention 1 technical scheme is 355 nanometers in excitation wavelength, and monitoring wavelength is the decay of luminescence curve of 430 nanometers.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
Embodiment 1:
Preparation Ca
1.998eu
0.002naSi
4o
10f
According to chemical formula Ca
1.998eu
0.002naSi
4o
10in F, the stoichiometric ratio of each element takes respectively calcium carbonate CaCO
3: 0.999 gram, europium sesquioxide Eu
2o
3: 0.004 gram, silicon-dioxide SiO
2: 2.404 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 500 DEG C, calcination time 3 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, the sintering that (is embedded in activated carbon powder) again in reducing atmosphere, and 700 DEG C of temperature, calcination time 7 hours, is then chilled to room temperature, takes out sample; Finally add Sodium Fluoride NaF:0.420 gram, Calcium Fluoride (Fluorspan) CaF
2: 0.281 gram, after fully being ground again, it is placed on reducing atmosphere sintering in retort furnace, and calcining temperature is 1000 DEG C, and calcination time is 10 hours, obtains powder shaped silicofluoride blue emitting material.
Referring to accompanying drawing 1, it is the X-ray powder diffraction collection of illustrative plates of the material sample prepared by the present embodiment technical scheme, and XRD test result shows, prepared material is silicofluoride Ca
2naSi
4o
10f monophase materials.
Referring to accompanying drawing 2, it is 0.1% concentration Eu
2+ion is at Ca
1.998eu
0.002naSi
4o
10in F fluorescent material, excite with near-ultraviolet light 395 nanometers the luminescent spectrum obtaining, the main center emission wavelength of this material is the blue-light-emitting wave band of approximately 450 nanometers, calculate by CIE simultaneously, the coordinate of learning it is x=0.172, y=0.161, also just in time drop on blue region, it can finely be applicable to the white light LEDs that near-ultraviolet light is excitation light source.
Referring to accompanying drawing 3, what obtain from material sample monitoring utilizing emitted light 450 nanometers to preparing by the technology of the present invention can find out the exciting light spectrogram of ultraviolet blue region, the blue-light-emitting of this material excite main near ultraviolet (NUV) region between 350～420 nanometers, source, can mate well near ultraviolet LED chip.
Referring to accompanying drawing 4, it is that the material sample of preparing by the present embodiment technical scheme is 355 nanometers at excitation wavelength, and monitoring optical wavelength is the decay of luminescence curve of 430 nanometers, and be 1.604 microseconds the fall time that can calculate this blue colour fluorescent powder from figure.
Embodiment 2:
Preparation Ca
1.98eu
0.02naSi
4o
10f
According to chemical formula Ca
1.98eu
0.02naSi
4o
10in F, the stoichiometric ratio of each element takes respectively calcium oxide CaO:0.550 gram, europium nitrate Eu (NO
3)
3: 0.068 gram, silicon-dioxide SiO
2: 2.404 grams, sodium oxide Na
2o:0.310 gram, after grinding and mixing, selects air atmosphere to calcine for the first time in agate mortar, and temperature is 300 DEG C, and calcination time 8 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, the sintering that (is embedded in activated carbon powder) again in reducing atmosphere, and 1000 DEG C of temperature, calcination time 4 hours, is then chilled to room temperature, takes out sample; Finally add Calcium Fluoride (Fluorspan) CaF
2: 0.281 gram, after fully being ground again, it is placed on reducing atmosphere sintering in retort furnace, and calcining temperature is 1200 DEG C, and calcination time is 5 hours, obtains powder shaped silicofluoride blue emitting material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Embodiment 3:
Preparation Ca
1.9eu
0.1naSi
4o
10f
According to chemical formula Ca
1.9eu
0.1naSi
4o
10in F, the stoichiometric ratio of each element takes respectively calcium carbonate CaCO
3: 0.901 gram, europium sesquioxide Eu
2o
3: 0.176 gram, silicon-dioxide SiO
2: 2.404 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 400 DEG C, calcination time 6 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, the sintering that (is embedded in activated carbon powder) again in reducing atmosphere, and 800 DEG C of temperature, calcination time 5 hours, is then chilled to room temperature, takes out sample; Finally add Sodium Fluoride NaF:0.420 gram, Calcium Fluoride (Fluorspan) CaF
2: 0.281 gram, after fully being ground again, it is placed on reducing atmosphere sintering in retort furnace, and calcining temperature is 1050 DEG C, and calcination time is 9 hours, obtains powder shaped silicofluoride blue emitting material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Embodiment 4:
Preparation Ca
1.8eu
0.2naSi
4o
10f
According to chemical formula Ca
1.8eu
0.2naSi
4o
10in F, the stoichiometric ratio of each element takes respectively calcium carbonate CaCO
3: 0.801 gram, europium nitrate Eu (NO
3)
3: 0.677 gram, silicon-dioxide SiO
2: 2.404 grams, sodium carbonate Na
2cO
3: 0.530 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 450 DEG C, calcination time 8 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, the sintering that (is embedded in activated carbon powder) again in reducing atmosphere, and 950 DEG C of temperature, calcination time 5 hours, is then chilled to room temperature, takes out sample; Finally add Calcium Fluoride (Fluorspan) CaF
2: 0.281 gram, after fully being ground again, it is placed on reducing atmosphere sintering in retort furnace, and calcining temperature is 1100 DEG C, and calcination time is 8 hours, obtains powder shaped silicofluoride blue emitting material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Embodiment 5:
Preparation Ca
1.5eu
0.5naSi
4o
10f
According to chemical formula Ca
1.5eu
0.5naSi
4o
10in F, the stoichiometric ratio of each element takes respectively calcium oxide CaO:0.281 gram, europium sesquioxide Eu
2o
3: 0.88 gram, silicon-dioxide SiO
2: 2.404 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 500 DEG C, calcination time 4 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, the sintering that (is embedded in activated carbon powder) again in reducing atmosphere, and 900 DEG C of temperature, calcination time 6 hours, is then chilled to room temperature, takes out sample; Finally add Sodium Fluoride NaF:0.420 gram, Calcium Fluoride (Fluorspan) CaF
2: 0.281 gram, after fully being ground again, it is placed on reducing atmosphere sintering in retort furnace, and calcining temperature is 1100 DEG C, and calcination time is 7 hours, obtains powder shaped silicofluoride blue emitting material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Claims (5)
1. a preparation method for silicofluoride blue colour fluorescent powder, the chemical formula of described silicofluoride blue colour fluorescent powder is Ca
2-2xeu
2xnaSi
4o
10f, wherein 0.0001 < x≤0.25; Under wavelength is 350～420 nanometers near ultraviolet excitated, launch the blue-fluorescence that main wavelength is 450～475 nanometers; It is characterized in that adopting high temperature solid-state method, comprise the following steps:
(1) to contain calcium ion Ca
2+compound, contain sodium ion Na
+compound, contain silicon ion Si
4+compound, europium ion Eu
3+for raw material, by molecular formula Ca
2-2xeu
2xnaSi
4o
10in F, the stoichiometric ratio of corresponding element takes each raw material, wherein 0.0001 < x≤0.25; The raw material taking is ground respectively, and remix is even, obtains mixture;
(2) other mixtures except fluorochemical are calcined under air atmosphere, calcining temperature is 100～500 DEG C, and calcination time is 1～10 hour;
(3) by the mixture naturally cooling after calcining, grind and mix, sintering in the atmosphere of reduction, described reducing atmosphere is active carbon granule reducing atmosphere, and calcining temperature is 600～1000 DEG C, and calcination time is 2～8 hours;
(4) by the mixture naturally cooling after calcining, add fluorochemical to grind and mix, sintering in the atmosphere of reduction; described reducing atmosphere is active carbon granule reducing atmosphere; calcining temperature is 800～1200 DEG C, and calcination time is 2～10 hours, obtains a kind of silicofluoride blue colour fluorescent powder.
2. the preparation method of a kind of silicofluoride blue colour fluorescent powder according to claim 1, is characterized in that: the described calcium ion Ca that contains
2+compound comprise the one in calcium oxide, calcium carbonate; Described fluorochemical comprises Calcium Fluoride (Fluorspan) or Calcium Fluoride (Fluorspan) and Sodium Fluoride.
3. the preparation method of a kind of silicofluoride blue colour fluorescent powder according to claim 1, is characterized in that: the described sodium ion Na that contains
+compound comprise the one in sodium oxide, sodium carbonate.
4. the preparation method of a kind of silicofluoride blue colour fluorescent powder according to claim 1, is characterized in that: the described silicon ion Si that contains
4+compound be silicon-dioxide; The described europium ion Eu that contains
3+compound oxidation europium, europium nitrate in one.
5. the preparation method of a kind of silicofluoride blue colour fluorescent powder according to claim 1, is characterized in that: the described calcining temperature of step (2) is 300～500 DEG C, and calcination time is 3～8 hours; The described calcining temperature of step (3) is 700～1000 DEG C, and calcination time is 4～7 hours; The described calcining temperature of step (4) is 1000～1200 DEG C, and calcination time is 5～10 hours.
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| CN104830343B (en) * | 2015-04-21 | 2017-03-22 | 内蒙古科技大学 | Fluorine boron silicate luminescent material and its preparation method |
| CN105694886B (en) * | 2015-12-23 | 2017-12-26 | 江苏师范大学 | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material |
| CN105482818B (en) * | 2015-12-23 | 2017-12-12 | 江苏师范大学 | Made of Eu2+Preparation method and application of activated blue fluoride fluorescent powder |
| CN106811197B (en) * | 2017-01-24 | 2019-01-11 | 江苏师范大学 | A kind of fluosilicic acid alkali up-conversion luminescence ceramic material and preparation method thereof |
| CN106947472B (en) * | 2017-01-24 | 2019-06-07 | 江苏师范大学 | A kind of fluosilicic acid alkali red fluorescence ceramic material, preparation method and application |
| CN107446573A (en) * | 2017-08-18 | 2017-12-08 | 苏州轻光材料科技有限公司 | A kind of UV excited white lights LED fluorescent material and preparation method thereof |
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| CN101336279A (en) * | 2005-12-02 | 2008-12-31 | 沙诺夫公司 | Metal silicate halide phosphors and led lighting devices using the same |
| CN102660263A (en) * | 2012-05-04 | 2012-09-12 | 苏州大学 | A kind of Eu2+ activated calcium chlorosilicate fluorescent powder, preparation method and application |
| CN102703066A (en) * | 2012-06-13 | 2012-10-03 | 中国计量学院 | Fluorosilicate fluorescent powder and preparation method thereof |
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| CN101336279A (en) * | 2005-12-02 | 2008-12-31 | 沙诺夫公司 | Metal silicate halide phosphors and led lighting devices using the same |
| CN102660263A (en) * | 2012-05-04 | 2012-09-12 | 苏州大学 | A kind of Eu2+ activated calcium chlorosilicate fluorescent powder, preparation method and application |
| CN102703066A (en) * | 2012-06-13 | 2012-10-03 | 中国计量学院 | Fluorosilicate fluorescent powder and preparation method thereof |
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