CN101486908A - Red long afterglow luminous material and preparing process thereof - Google Patents
Red long afterglow luminous material and preparing process thereof Download PDFInfo
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- CN101486908A CN101486908A CNA2009100940798A CN200910094079A CN101486908A CN 101486908 A CN101486908 A CN 101486908A CN A2009100940798 A CNA2009100940798 A CN A2009100940798A CN 200910094079 A CN200910094079 A CN 200910094079A CN 101486908 A CN101486908 A CN 101486908A
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 230000005923 long-lasting effect Effects 0.000 claims abstract 6
- 229910001940 europium oxide Inorganic materials 0.000 claims abstract 5
- 239000011593 sulfur Substances 0.000 claims abstract 3
- 239000011734 sodium Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 10
- 239000012190 activator Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 abstract 2
- 229940075613 gadolinium oxide Drugs 0.000 abstract 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 230000002688 persistence Effects 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
一种红色长余辉发光材料及其制备，以Gd2O2S为基质，Eu3+为激活剂，适量掺杂TiO2，MgO与TiO2共掺杂，SiO2与TiO2共掺杂。其组成为Gd2O2S:Eu3+，Ti4+；Gd2O2S:Eu3+，Mg2+，Ti4+或Gd2O2S:Eu3+，Si4+，Ti4+。制备该发光材料的各原料的质量百分含量分别为：氧化钆：32.27％～33.98％，氧化铕：1.02％～2.73％，硫磺：32.0％～38.0％，无水碳酸钠：23.1％～28.2％，碳酸锂：3.9％～4.8％，氧化镁：0～0.58％，二氧化硅：0～0.87％，二氧化钛：0.19％～1.15％，并且氧化钆与氧化铕的摩尔比：
A red long-lasting luminescent material and its preparation. Gd 2 O 2 S is used as a matrix, Eu 3+ is used as an activator, an appropriate amount of TiO 2 is doped, MgO and TiO 2 are co-doped, and SiO 2 and TiO 2 are co-doped. Its composition is Gd 2 O 2 S:Eu 3+ , Ti 4+ ; Gd 2 O 2 S:Eu 3+ , Mg 2+ , Ti 4+ or Gd 2 O 2 S:Eu 3+ , Si 4+ , Ti 4+ . The mass percentages of the raw materials used to prepare the luminescent material are: gadolinium oxide: 32.27% to 33.98%, europium oxide: 1.02% to 2.73%, sulfur: 32.0% to 38.0%, anhydrous sodium carbonate: 23.1% to 28.2% %, lithium carbonate: 3.9% to 4.8%, magnesium oxide: 0 to 0.58%, silicon dioxide: 0 to 0.87%, titanium dioxide: 0.19% to 1.15%, and the molar ratio of gadolinium oxide to europium oxide:
Description
Technical field
The present invention relates to a kind of novel red long after glow luminous material and preparation method thereof, be specifically related to Gd
2O
2S is a matrix, Eu
3+Be activator, an amount of doped Ti O
2, MgO and TiO
2Codoped, or SiO
2With TiO
2Red long afterglow luminous material of codoped and preparation method thereof belongs to the luminescent material technical field.
Background technology
Nontoxic, harmless, "dead" and fluorescent lifetime is long, luminosity is high, stability of material is good advantage that rare earth long-afterglow luminescent material has, have characteristics energy-conservation, that can be recycled, be a class photo-induced energy storage functional materials, be widely used in fields such as low light level illumination, emergent pilot lamp, building decoration, industrial art, information storage and energetic ray detection.At present, blue-greenish colour and yellow-green colour long-afterglow material mainly are rare earth doped aluminate and silicate, and luminescent properties such as its luminosity and time of persistence have reached practical application and need and realize suitability for industrialized production; For example, Patent Office of the People's Republic of China's invention disclosed name is called " a kind of aluminate luminescent material and preparation thereof " (number of patent application: be exactly a kind of rear-earth-doped aluminate long after glow luminous material 200710044112.7), this material is with Eu
2+Activate, have long, good luminescent properties such as luminosity is high, stability of material is good of afterglow time.This class long after glow luminous material has been subjected to the single restriction of the color development of material own, the color of the after-glow light that it sent is blue-greenish colour and yellow-green colour, although handle the change that can cause glow color by various dyeing, but, because the characteristic of the dyestuff that coats itself, the dyestuff of these coatings can not use under the pyritous condition.
The red long afterglow luminous material of efficient stable is the emphasis that the researchist pays close attention to and develops always, the denomination of invention of authorizing as Patent Office of the People's Republic of China is " long persistence luminous sulfide material and manufacture method " (patent No.: patent 97111381.5), introduced a kind of red long afterglow luminous material MS:Eu, A, B, activator are Eu
3+, but feature limits such as its instability, weathering resistance difference its application.Another denomination of invention that Patent Office of the People's Republic of China is authorized be " red rare-earth phosphorescent body with long afterglow " (patent No.: patented technology 02125512.1), a kind of rare-earth red long persistence phosphor is disclosed, chemical constitution is Y
2O
2S:Sm, Mg, Ti.Adopt Y
2O
3With S as base starting material, Na
2CO
3As fusing assistant, Sm
3+Be exciting agent, Mg
2+And Ti
4+As being total to exciting agent, gac is as reductive agent, and product high temperature is come out of the stove, hot salt acid soak 1.5～2.0h, hot wash.The emission peak of this material is positioned at 607.9nm～608nm, and color is orange red partially.In this patent and not mentioned all the other brightness times, and colourity is impure, and is still far away apart from practical application, remains further research.In addition, use hydrochloric acid soln in its preparation process, environment is produced pollute.And with Gd
2O
2S is the long after glow luminous material of matrix, rarely has report at present.
Summary of the invention
An object of the present invention is synthetic a kind of novel red long afterglow luminous material, this material is with Gd
2O
2S is a matrix, Eu
3+Be activator, an amount of doped Ti O
2, or MgO and TiO
2Codoped, or SiO
2With TiO
2The long after glow luminous material of codoped; The surplus light that sends shows that pure red is luminous, and the brightness height of surplus light, and time of persistence is long.Another object of the present invention is to provide a kind of preparation method of above-mentioned luminescent material,, and environment do not produced harmful effect with the red long afterglow luminous material of present method preparation, not only stable performance.
The object of the present invention is achieved like this:
Synthetic luminescent material of the present invention consists of Gd
2O
2S:Eu
3+, Ti
4+, being hexagonal system structure, emission wavelength is about 627nm, through sunlight or fluorescent light irradiation, sends pure ruddiness, has significant long-persistence luminous characteristic.
It is gadolinium sesquioxide (Gd that the present invention prepares the used substrate material of above-mentioned luminescent material
2O
3), sulphur (S), activator is europium sesquioxide (Eu
2O
3), fusing assistant is anhydrous sodium carbonate (Na
2CO
3), Quilonum Retard (Li
2CO
3), doping agent is titanium dioxide (TiO
2), above-mentioned materials is by behind its quantitative mixing, and the preparation of phosphorescent substance is carried out under heating calcination state.
In order to increase trap depth, prolong time of persistence, luminescent material of the present invention is formed more preferably Gd
2O
2S:Eu
3+, Mg
2+, Ti
4+Or Gd
2O
2S:Eu
3+, Si
4+, Ti
4+Prepare the used matrix of its luminescent material except that same with above-mentioned matrix phase, its doping agent has also increased magnesium oxide (MgO) and silicon-dioxide (SiO respectively
2).
Preparation method of the present invention is: it is gadolinium sesquioxide (Gd that the present invention prepares the used raw material of above-mentioned long after glow luminous material
2O
3), europium sesquioxide (Eu
2O
3), sulphur (S), anhydrous sodium carbonate (Na
2CO
3), Quilonum Retard (Li
2CO
3), magnesium oxide (MgO), silicon-dioxide (SiO
2), titanium dioxide (TiO
2); The quality percentage composition of each raw material is respectively: gadolinium sesquioxide (Gd
2O
3): 32.27%～33.98%, europium sesquioxide (Eu
2O
3): 1.02%～2.73%, sulphur (S): 32.0%～38.0%, anhydrous sodium carbonate (Na
2CO
3): 23.1%～28.2%, Quilonum Retard (Li
2CO
3): 3.9%～4.8%, magnesium oxide (MgO): 0～0.58%, silicon-dioxide (SiO
2): 0～0.87%, titanium dioxide (TiO
2): 0.19%～1.15%, and gadolinium sesquioxide (Gd
2O
3) and europium sesquioxide (Eu
2O
3) the ratio (mol ratio) of amount of substance be n
(Gd2O3): n
(Eu2O3=11.50～32.33.Its preparation process is: after selected raw material is accurately taken by weighing according to aforementioned proportion, fully grind mixing in agate mortar, be pressed into the suitable sheet of size with tabletting machine, put into corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 350 ℃ of insulation 20～30min, 1240 ℃～1280 ℃ insulation 2.0～3.0h are cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 90 ℃～110 ℃ freeze-day with constant temperature 3.0h～5.0h can obtain the white powder product in thermostatic drying chamber.
Reaction mechanism of the present invention is:
(1)Na
2CO
3+S→Na
2S+Na
2S
x+CO
2
Na
2S+Na
2S
x+Gd
2O
3+Eu
2O
3+TiO
2→Gd
2O
2S:Eu
3+，Ti
4+
(2)Na
2CO
3+S→Na
2S+Na
2S
x+CO
2
Na
2S+Na
2S
x+Gd
2O
3+Eu
2O
3+MgO+TiO
2→Gd
2O
2S:Eu
3+，Mg
2+，Ti
4+
(3)Na
2CO
3+S→Na
2S+Na
2S
x+CO
2
Na
2S+Na
2S
x+Gd
2O
3+Eu
2O
3+TiO
2+SiO
2→Gd
2O
2S:Eu
3+，Si
4+，Ti
4+
The invention has the beneficial effects as follows: because long after glow luminous material of the present invention adopts Eu
3+As activator, emission peak is positioned at the 627nm place, and colourity is purer, shows that pure red is luminous.The substrate material of long after glow luminous material of the present invention is selected highly stable, the resistant to elevated temperatures Gd of chemical property for use
2O
2S, Gd simultaneously
2O
2S and Eu
3+Have very high energy transfer efficiency, help stimulated luminescence, after the doped metal ion, the brightness height that is sent, colourity is pure, and obviously prolong time of persistence, and improved crystalline structure simultaneously.Do not use hydrochloric acid soln among the preparation method of long after glow luminous material of the present invention, environment is not almost polluted.
Description of drawings:
Fig. 1 is that embodiment 1 makes sample sample Gd
2O
2S:Eu
3+, Ti
4+XRD figure spectrum;
Fig. 2 is that embodiment 2 makes sample sample Gd
2O
2S:Eu
3+, Mg
2+, Ti
4+Emmission spectrum;
Fig. 3 is that embodiment 3 makes sample sample Gd
2O
2S:Eu
3+, Si
4+, Ti
4+The SEM photo.
Embodiment
Below in conjunction with the invention will be further described in conjunction with example:
Embodiment 1
Proportioning raw materials:
Material name: quality: shared mass percent:
Gadolinium sesquioxide (Gd
2O
3) 11.6545g 33.43%
Europium sesquioxide (Eu
2O
3) 0.5955g 1.71%
Sulphur (S) 12.2500g 35.14%
Anhydrous sodium carbonate (Na
2CO
3) 8.7475g 25.09%
Quilonum Retard (Li
2CO
3) 1.4821g 4.25%
Titanium dioxide (TiO
2) 0.1352g 0.39%
Fully grind in agate mortar, mixing is pressed into the suitable sheet of size with tabletting machine, put into corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 350 ℃ of insulation 20min, 1240 ℃ of insulation 3.0h, be cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 110 ℃ of freeze-day with constant temperature 3.0h in thermostatic drying chamber can obtain white powder sample Gd
2O
2S:Eu
3+, Ti
4+Identify through X-ray diffraction, as shown in Figure 1, the diffraction peak data and the Gd of obtained sample
2O
2(card number: diffraction data basically identical 26-1422) illustrates the crystalline structure and the Gd of obtained sample to the JCPDS standard card of S
2O
2S is identical, belongs to hexagonal system.Luminescent spectrum is measured and to be shown: emission peak wavelength is about 627nm, and through ultraviolet lamp or visible light (as sunlight and fluorescent lamp) irradiation, this luminescent material presents strong red long-afterglow emission, and brightness height, colourity are pure.
Proportioning raw materials:
Material name: quality: shared mass percent:
Gadolinium sesquioxide (Gd
2O
3) 11.6545g 33.30%
Europium sesquioxide (Eu
2O
3) 0.5955g 1.70%
Sulphur (S) 12.2500g 35.00%
Anhydrous sodium carbonate (Na
2CO
3) 8.6319g 24.66%
Quilonum Retard (Li
2CO
3) 1.4625g 4.18%
Magnesium oxide (MgO) 0.1352g 0.39%
Titanium dioxide (TiO
2) 0.2704g 0.77%
Fully grind in agate mortar, mixing is pressed into the suitable sheet of size with tabletting machine, put into little corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 300 ℃ of insulation 30min, 1280 ℃ of insulation 2.0h, be cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 90 ℃ of freeze-day with constant temperature 5.0h in thermostatic drying chamber can obtain white powder sample Gd
2O
2S:Eu
3+, Mg
2+, Ti
4+Identify the crystalline structure of this product and Gd through X-ray diffraction
2O
2S is identical, belongs to hexagonal system.The emmission spectrum of sample as shown in Figure 2, as seen: emission peak master peak value wavelength is about 627nm, and its intensity is better than other peak value far away, and through ultraviolet lamp or visible light (as sunlight and fluorescent lamp) irradiation, this luminescent material presents bright pure red steady persistence emission.
Embodiment 3
Proportioning raw materials:
Material name: quality: shared mass percent:
Gadolinium sesquioxide (Gd
2O
3) 11.6545g 33.30%
Europium sesquioxide (Eu2O
3) 0.5955g 1.70%
Sulphur (S) 12.2500g 35.00%
Anhydrous sodium carbonate (Na2CO
3) 8.5741g 24.50%
Quilonum Retard (Li
2CO
3) 1.4527g 4.15%
Silicon-dioxide (SiO
2) 0.2028g 0.58%
Titanium dioxide (TiO
2) 0.2704g 0.77%
Fully grind in agate mortar, mixing is pressed into the suitable sheet of size with tabletting machine, put into little corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 330 ℃ of insulation 25min, 1250 ℃ of insulation 2.5h, be cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 100 ℃ of freeze-day with constant temperature 4.0h in thermostatic drying chamber can obtain white powder sample Gd
2O
2S:Eu
3+, Si
4+, Ti
4+Identify the crystalline structure of this product and Gd through X-ray diffraction
2O
2S is identical, belongs to hexagonal system.Luminescent spectrum is measured and shown: emission peak main peak value wavelength is about 627nm.Accompanying drawing 3 is the SEM photo of preparation sample, and as seen: the pattern of this sample particle is the class sphere, and crystalline structure is intact, favorable dispersity, and size is between 5～12 μ m.Through the irradiation of ultraviolet lamp or visible light (as sunlight and fluorescent lamp), this luminescent material presents strong red long-afterglow emission, and brightness height, colourity are pure.
Claims (4)
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100940798A CN101486908A (en) | 2009-02-04 | 2009-02-04 | Red long afterglow luminous material and preparing process thereof |
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|---|---|
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ID=40889973
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|---|---|---|---|---|
| CN102352250A (en) * | 2011-07-22 | 2012-02-15 | 彩虹集团电子股份有限公司 | Method for preparing green gadolinium terbium oxysulfide phosphor |
| CN103194234A (en) * | 2013-04-12 | 2013-07-10 | 天津理工大学 | Blue light excited solid solution fluorescent material |
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2009
- 2009-02-04 CN CNA2009100940798A patent/CN101486908A/en active Pending
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| CN102352250A (en) * | 2011-07-22 | 2012-02-15 | 彩虹集团电子股份有限公司 | Method for preparing green gadolinium terbium oxysulfide phosphor |
| CN103194234A (en) * | 2013-04-12 | 2013-07-10 | 天津理工大学 | Blue light excited solid solution fluorescent material |
| CN106047346A (en) * | 2016-05-30 | 2016-10-26 | 南京信息工程大学 | Red fluorescent material for AC-LED and preparation method thereof |
| CN106047346B (en) * | 2016-05-30 | 2018-11-16 | 南京信息工程大学 | A kind of red fluorescence material and preparation method thereof for AC-LED |
| CN113621365A (en) * | 2021-09-10 | 2021-11-09 | 江苏师范大学 | A kind of preparation method of europium-doped red silicate fluorescent material with high luminescence intensity |
| CN113684575A (en) * | 2021-09-18 | 2021-11-23 | 桐乡市华家那羊绒服饰有限公司 | Antibacterial cashmere knitted yarn and preparation method thereof |
| CN113684575B (en) * | 2021-09-18 | 2022-07-01 | 桐乡市华家那羊绒服饰有限公司 | Antibacterial cashmere knitted yarn and preparation method thereof |
| CN117801820A (en) * | 2023-12-28 | 2024-04-02 | 广州珠江光电新材料有限公司 | Red long afterglow material and preparation method thereof |
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