CN101735810B - Method for preparing rare-earth doped dodecacalcium heptaluminate light-accumulating luminescent powder emitting indigo light - Google Patents
Method for preparing rare-earth doped dodecacalcium heptaluminate light-accumulating luminescent powder emitting indigo light Download PDFInfo
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- CN101735810B CN101735810B CN200910256008.3A CN200910256008A CN101735810B CN 101735810 B CN101735810 B CN 101735810B CN 200910256008 A CN200910256008 A CN 200910256008A CN 101735810 B CN101735810 B CN 101735810B
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- 239000000843 powder Substances 0.000 title claims abstract description 46
- 235000000177 Indigofera tinctoria Nutrition 0.000 title claims abstract description 14
- 229940097275 indigo Drugs 0.000 title claims abstract description 14
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 20
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 229910021538 borax Inorganic materials 0.000 claims description 8
- 239000004328 sodium tetraborate Substances 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005049 combustion synthesis Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000006184 cosolvent Substances 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 78
- 229910052693 Europium Inorganic materials 0.000 description 14
- 238000000695 excitation spectrum Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003746 solid phase reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 230000002688 persistence Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 3
- -1 constantly stir Chemical compound 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing rare-earth doped dodecacalcium heptaluminate light-accumulating luminescent powder emitting indigo light, which belongs to the technical field of luminous materials. The method comprises the following steps: preparing mixed metallic nitrate solution containing Ca2+, Al3+, Eu3+ and Re3+ (Re is Dy, Nd or La) in a molar ratio of the chemical general formula Ca12-x-yAl14O33: Eux, Rey (Re is Dy, Nd or La) (x is 0.06 to 0.96 and y is 0.06 to 1.20); adding a cosolvent and a fuel into the solution in turn, then adding proper amount of deionized water into the solution, and stirring the solution continuously to fully dissolve the solid so as to obtain transparent solution; then dripping diluent nitric acid solution into the transparent solution till the pH of the transparent solution is between 5 and 7 so as to obtain reaction solution; and preserving the heat of the reaction solution for 5 to 10 minutes at the temperature of between 500 and 750 DEG C under the air atmosphere, then performing a burning synthesis reaction, cooling a reaction product to the room temperature, and grinding the reaction product to obtain the light-accumulating luminescent powder of the invention. The method has the advantages of low synthesizing temperature and high yield, and is suitable for batch preparation.
Description
Technical field
The invention belongs to the luminescent material technical field, relate to a kind of rare earth doped C 12 A 7 (Ca
12Al
14O
33: Eu, Re) preparation method of light-accumulating luminescent powder, the Ca that relate in particular to that a kind of preparation technology is simple, synthesis temperature is low, sends out coloured light indigo
12Al
14O
33: Eu, the burning synthesis for preparing Preparation Method of Re (Re=Dy, Nd, La) light-accumulating luminescent powder.
Background technology
Light-storing and emitting material has referred to absorbed and has excited luminous energy and stored, after exciting light stops to shine this material, again the energy that stores with the form slow release of light out, and the luminescent material of luminous sustainable for some time.Its Application Areas is very extensive, is widely used in the fields such as building decoration, communications and transportation, security against fire, artwork, has huge marketable value and social benefit.Light-storing and emitting material take aluminate as matrix has the advantages that luminous color is abundant, chemical stability is good, do not add radioelement, has been subject to people's great attention.At present, aluminate is that the light-storing and emitting material of the comparative maturity of matrix has: the CaAl of the purple light that turns blue
2O
4: Eu, Nd, the Sr of the green glow that turns blue
4Al
14O
25: Eu, the SrAl of Dy and jaundice green glow
2O
4: Eu, Dy.
In addition, the research and development aluminate is that other light-storing and emitting material of matrix receives much attention always.The people such as Zhang adopted high-temperature solid phase reaction method to synthesize in 2003 to send out indigo the Ca of coloured light
12Al
14O
33: Eu, Nd, the method is with CaCO
3, Al
2O
3, Eu
2O
3And Nd
2O
3Be raw material, the pressed powder raw material was dispersed in water ball milling after 4 hours, be placed in the baking oven dry several hours and obtain dry powder, then adopt nitrogen (97%, volume ratio) with hydrogen (3%, volume ratio) gas mixture was calcined the Ca that is synthesized to gained dry powder 3 hours at 1200 ℃ as week reduction gas
12Al
14O
33: Eu, Nd powder time of persistence is 50 seconds.But the high-temperature solid phase reaction method existence is not only consumed energy but also time-consuming, is needed to use hydrogen thereby have certain shortcomings such as danger.
Goal of the invention and content
Prepare Ca for high-temperature solid phase reaction method
12Al
14O
33: Eu, the shortcoming that Nd exists, be that pressed powder raw material ball milling mixing, sintering temperature are higher, the gas mixture that needs nitrogen and hydrogen causes the method not only to consume energy as weak reducing gas but also time-consuming and have certain problems such as danger, the object of the present invention is to provide a kind of Ca that sends out coloured light indigo
12Al
14O
33: Eu, Re (Re=Dy, Nd, La) light-accumulating luminescent powder fast, preparation method significantly energy-conservation, simple to operate, namely adopt combustion synthesis method to prepare Ca
12Al
14O
33: Eu, the method for Re (Re=Dy, Nd, La) light-accumulating luminescent powder.
The whole wiring solution-formings of raw material that the present invention uses are very easy to mix; Synthesis temperature is low; Adopt air atmosphere, therefore without dangerous, convenient and swift, obvious energy conservation, simple to operate, and output is high, is easy to realize batch production.
Purpose of the present invention can be realized by following technical scheme.
The Ca that the present invention sends out coloured light indigo
12Al
14O
33: Eu, the preparation method of Re (Re=Dy, Nd, La) light-accumulating luminescent powder adopts following processing step:
(1) according to chemical general formula Ca
12-x-yAl
14O
33: Eu
x, Re
yThe mol ratio of (Re=Dy, Nd, La) (x=0.06～0.96, y=0.06～1.20) is mixed with and contains Ca
2+, Al
3+, Eu
3+, Re
3+The hybrid metal nitrate solution of (Re=Dy, Nd, La).
(2) in described hybrid metal nitrate solution, add successively fusing assistant and fuel, add again deionized water, constantly stir, the fusing assistant of adding and fuel are dissolved fully, obtain clear solution.
(3) under the strong stirring, in described clear solution, drip dilute nitric acid solution, until the pH of clear solution till between 5～7, obtains reaction solution.
(4) under air atmosphere, described reaction solution was carried out combustion synthesis reaction in 5～10 minutes in 500～750 ℃ of lower insulations, be cooled to that room temperature is loosened, the spumescence product, can obtain light-accumulating luminescent powder of the present invention after the grinding.
Wherein, described hybrid metal nitrate solution is the mixing solutions of ca nitrate soln, aluminum nitrate solution, europium nitrate solution, Dysprosium trinitrate solution (or neodymium nitrate solution or lanthanum nitrate hexahydrate).Described fusing assistant is boric acid or borax, B behind control adding boric acid or the borax
3+With Al
3+Mol ratio be between 5～15%; Described fuel is urea or carbohydrazide, and its consumption (mole number) is 4～12 times of hybrid metal nitrate total mole number.
Among the present invention, the effect of fusing assistant (boric acid or borax): heating becomes B in acidic solution
2O
3, B
2O
3By promoting the formation of C 12 A 7 crystalline phase, reduce synthesis temperature.Simultaneously, can promote rare earth element to enter the C 12 A 7 lattice to form luminescence center and Trapping Centers.Under air atmosphere, carry out redox reaction between metal nitrate and urea or the carbohydrazide, produce some gases with reductibility and make the trivalent europium be reduced to divalent europium, make the present invention not need other reducing gas.
Specifically:
With a certain amount of Ca (NO
3)
24H
2O, Al (NO
3)
39H
2O is mixed with certain density solution with deionized water dissolving respectively.With Eu
2O
3, Dy
2O
3, Nd
2O
3And La
2O
3Respectively with dilute nitric acid solution dissolving and be mixed with certain density Eu (NO
3)
3, Dy (NO
3)
3, Nd (NO
3)
3And La (NO
3)
3Solution.According to chemical general formula Ca
12-x-yAl
14O
33: Eu
x, Re
yThe mol ratio of (Re=Dy, Nd, La) (x=0.06～0.96, y=0.06～1.20) is mixed with and contains Ca
2+, Al
3+, Eu
3+, Re
3+The hybrid metal nitrate solution of (Re=Dy, Nd, La).
In above-mentioned hybrid metal nitrate solution, add successively a certain amount of fusing assistant (boric acid or borax) and a certain amount of fuel (urea or carbohydrazide), add again appropriate amount of deionized water, constantly stir, fusing assistant (boric acid or borax), the fuel (urea or carbohydrazide) of adding are dissolved fully, obtain clear solution.Then, under the strong stirring, in above-mentioned clear solution, drip dilute nitric acid solution, until the pH of clear solution till between 5～7, obtains reaction solution.
Above-mentioned reaction solution is shifted in crucible, then put in the retort furnace that is preheating to 500～750 ℃, under air atmosphere, be incubated 5～10 minutes and carry out combustion synthesis reaction, be cooled to that room temperature is loosened, the spumescence product, obtain Ca of the present invention after the grinding
12-x-yAl
14O
33: Eu
x, Re
y(Re=Dy, Nd, La) light-accumulating luminescent powder.
The present invention compared with prior art has following technological merit:
(1) the present invention has synthesized Ca under lower temperature (500～750 ℃)
12Al
14O
33: Eu, Re (Re=Dy, Nd, La) light-accumulating luminescent powder, synthesis temperature is lower 450～700 ℃ than high-temperature solid phase reaction method, and whole reaction process only needs 5～10 minutes, has obvious energy conservation, characteristics conveniently.
(2) the present invention has three kinds of rare earth elements to can be used as the codoped element of Eu element, and namely any one in Dy, Nd, three kinds of elements of La all can.
(3) compare with high-temperature solid phase reaction method, the present invention adopts air atmosphere, and does not need the mixed gas of nitrogen and hydrogen to do weak reducing gas.
(4) the prepared Ca of the present invention
12Al
14O
33: Eu, Re (Re=Dy, Nd, La) light-accumulating luminescent powder is all launched indigo coloured light, and luminescence peak all is positioned at 440nm.Product output is high, is easy to realize in batches preparation.
Description of drawings
Fig. 1 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the XRD figure of Dy powder
Fig. 2 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the excitation spectrum of Dy powder
Fig. 3 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the emmission spectrum of Dy powder
Fig. 4 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the decay of afterglow curve of Dy powder
Fig. 5 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the XRD figure of Nd powder
Fig. 6 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the excitation spectrum of Nd powder
Fig. 7 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the emmission spectrum of Nd powder
Fig. 8 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the decay of afterglow curve of Nd powder
Fig. 9 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the XRD figure of La powder
Figure 10 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the excitation spectrum of La powder
Figure 11 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the emmission spectrum of La powder
Figure 12 is by the Ca of the inventive method preparation
12Al
14O
33: Eu, the decay of afterglow curve of La powder
Embodiment
Embodiment 1:
(1) according to chemical general formula Ca
12-x-yAl
14O
33: Eu
x, Dy
yThe mol ratio of (x=0.12, y=0.24) is mixed with and contains Ca
2+, Al
3+, Eu
3+, Dy
3+The hybrid metal nitrate solution.Specifically:
In stink cupboard, with 0.4399g Eu
2O
3Put into beaker, then add the dilute nitric acid solution of 37.5mL 0.20mol/L in the beaker, constantly stir, until complete reaction, then be mixed with the Eu (NO of 0.01mol/L
3)
3Solution is with for subsequent use.With 0.9325g Dy
2O
3Put into beaker, then add the dilute nitric acid solution of 75mL 0.20mol/L in the beaker, constantly stir, until complete reaction, then be mixed with the Dy (NO of 0.02mol/L
3)
3Solution is with for subsequent use.
Take by weighing respectively 4.1232g Ca (NO
3)
24H
2O, 7.8777g Al (NO
3)
39H
2O puts into beaker, adds the 80mL deionized water, constantly stirs, and it is dissolved fully.Then, the Eu (NO that adds 18mL 0.01mol/L
3)
3Dy (the NO of solution and 18mL 0.02mol/L
3)
3Solution constantly stirs, and solution is mixed, and obtains meeting chemical general formula Ca
11.64Eu
0.12Dy
0.24Al
14O
33Contain Ca
2+, Al
3+, Eu
3+, Dy
3+The hybrid metal nitrate solution.
(2) add 0.18g boric acid in the hybrid metal nitrate solution as fusing assistant, and then add 14.42g urea and act as a fuel, add again the 40mL deionized water, constantly stir, boric acid, urea are dissolved fully, obtain clear solution.
(3) under the strong stirring, drip the dilute nitric acid solution of 3 0.2mol/L in the above-mentioned clear solution, the pH that records solution is 7, stops to drip dilute nitric acid solution, obtains reaction solution.
(4) above-mentioned reaction solution is shifted in corundum crucible, then put in the retort furnace that is preheating to 500 ℃, under air atmosphere, be incubated 5 minutes and carry out combustion synthesis reaction, be cooled to that room temperature is loosened, the spumescence product, obtain Ca after the grinding
11.64Eu
0.12Dy
0.24Al
14O
33(referred to as Ca
12Al
14O
33: Eu, Dy) the light-accumulating luminescent powder.
Accompanying drawing 1 is the XRD figure of products therefrom.As can be seen from the figure each diffraction peak and standard card JCPDS No.09-0413 meet, and show that products therefrom has the crystalline structure of body-centered cubic C 12 A 7, and do not have other dephasign to occur.
(5) luminescent properties test
Accompanying drawing 2 is prepared Ca
12Al
14O
33: Eu, the excitation spectrum of Dy light-accumulating luminescent powder (the monitoring wavelength is 440nm), as can be seen from the figure, excitation spectrum is comprised of a Broad excitation band, wavelength region is 280～420nm, excites peak value to be positioned at 335nm, illustrates that ultraviolet ray and purple light can make it effectively be excited and luminous.Accompanying drawing 3 is prepared Ca
12Al
14O
33: Eu, the emmission spectrum of Dy light-accumulating luminescent powder (usefulness 335nm's is ultraviolet ray excited) can find out that from accompanying drawing 3 its emmission spectrum is wide emission band, and wavelength region is 390～530nm, and luminescence peak is positioned at 440nm, and glow color is indigo.Accompanying drawing 4 is Ca
12Al
14O
33: Eu, the decay of afterglow curve of Dy light-accumulating luminescent powder.Can find out that from accompanying drawing 4 after-glow brightness decays to 0.32mcd/m
2The time time of persistence be 109 seconds, show Ca
12Al
14O
33: Eu, Dy are light-storing and emitting materials.
Embodiment 2:
(1) according to chemical general formula Ca
12-x-yAl
14O
33: Eu
x, Nd
yThe mol ratio of (x=0.24, y=0.48) is mixed with and contains Ca
2+, Al
3+, Eu
3+, Nd
3+The hybrid metal nitrate solution.Specifically:
In stink cupboard, with 0.4399g Eu
2O
3Put into beaker, then add the dilute nitric acid solution of 37.5mL 0.20mol/L in the beaker, constantly stir, until complete reaction, then be mixed with the Eu (NO of 0.01mol/L
3)
3Solution is with for subsequent use.With 0.8412g Nd
2O
3Put into beaker, then add the dilute nitric acid solution of 75mL 0.20mol/L in the beaker, constantly stir, until complete reaction, then be mixed with the Nd (NO of 0.02mol/L
3)
3Solution is with for subsequent use.
Take by weighing respectively 3.9957g Ca (NO
3)
24H
2O, 7.8777g Al (NO
3)
39H
2O puts into beaker, adds the 70mL deionized water, constantly stirs, and it is dissolved fully.Then, the Eu (NO that adds 36mL 0.01mol/L
3)
3Nd (the NO of solution and 36mL 0.02mol/L
3)
3Solution constantly stirs, and solution is mixed, and obtains meeting chemical general formula Ca
11.28Eu
0.24Nd
0.48Al
14O
33Contain Ca
2+, Al
3+, Eu
3+, Nd
3+The hybrid metal nitrate solution.
(2) in above-mentioned hybrid metal nitrate solution, add the 0.12g borax as fusing assistant, and then measure in the 14.86g carbohydrazide adding beaker, act as a fuel, add again the 40mL deionized water, constantly stir, borax and carbohydrazide are dissolved fully, obtain clear solution.
(3) drip the dilute nitric acid solution of 3.2mL 0.2mol/L in the above-mentioned clear solution, the pH that records solution is 5, stops to drip dilute nitric acid solution, and constantly stirred solution obtains reaction solution.
(4) above-mentioned reaction solution is shifted in crucible, then put in the retort furnace that is preheating to 600 ℃, under air atmosphere, be incubated 8 minutes and carry out combustion synthesis reaction, be cooled to that room temperature is loosened, the spumescence product, obtain Ca after the grinding
11.28Eu
0.24Nd
0.48Al
14O
33(referred to as Ca
12Al
14O
33: Eu, Nd) the light-accumulating luminescent powder.
The XRD figure of products therefrom is seen accompanying drawing 5.Can find out that from accompanying drawing 5 each diffraction peak and standard card JCPDS No.09-0413 meet, show that products therefrom has the crystalline structure of body-centered cubic C 12 A 7, and not have other dephasign to occur.
(5) luminescent properties test
Accompanying drawing 6 is prepared Ca
12Al
14O
33: Eu, the excitation spectrum of Nd light-accumulating luminescent powder (the monitoring wavelength is 440nm) can be found out from accompanying drawing 6, excitation spectrum is comprised of a Broad excitation band, wavelength region is 280～420nm, excites peak value to be positioned at 335nm, illustrates that ultraviolet ray and purple light can make it effectively be excited and luminous.Accompanying drawing 7 is prepared Ca
12Al
14O
33: Eu, the emmission spectrum of Nd light-accumulating luminescent powder (usefulness 335nm's is ultraviolet ray excited) can find out that from accompanying drawing 7 its emmission spectrum is wide emission band, and wavelength region is 390～530nm, and luminescence peak is positioned at 440nm, and glow color is indigo.Accompanying drawing 8 is Ca
12Al
14O
33: Eu, the decay of afterglow curve of Nd light-accumulating luminescent powder.To find out, after-glow brightness decays to 0.32mcd/m from accompanying drawing 8
2The time time of persistence be 96 seconds, show Ca
12Al
14O
33: Eu, Nd are light-storing and emitting materials.
Embodiment 3:
(1) according to chemical general formula Ca
12-x-yAl
14O
33: Eu
x, La
yThe mol ratio of (x=0.60, y=1.08) is mixed with and contains Ca
2+, Al
3+, Eu
3+, La
3+The hybrid metal nitrate solution.Specifically:
In stink cupboard, with 0.4399g Eu
2O
3Put into beaker, then add the dilute nitric acid solution of 37.5mL 0.20mol/L in the beaker, constantly stir, until complete reaction, then be mixed with the Eu (NO of 0.025mol/L
3)
3Solution is with for subsequent use.With 0.8146g La
2O
3Put into beaker, then add the dilute nitric acid solution of 75mL 0.20mol/L in the beaker, constantly stir, until complete reaction, then be mixed with the La (NO of 0.05mol/L
3)
3Solution is with for subsequent use.
Take by weighing respectively 3.6556g Ca (NO
3)
24H
2O, 7.8777gAl (NO
3)
39H
2O puts into beaker, adds the 60mL deionized water, constantly stirs, and it is dissolved fully.Then, the Eu (NO that adds 36mL 0.025mol/L
3)
3La (the NO of solution and 32.4mL0.05mol/L
3)
3Solution constantly stirs, and solution is mixed, and obtains meeting chemical general formula Ca
10.32Eu
0.60La
1.08Al
14O
33Contain Ca
2+, Al
3+, Eu
3+, La
3+The hybrid metal nitrate solution.
(2) in above-mentioned hybrid metal nitrate solution, add successively 0.20g boric acid as fusing assistant, and 21.34g urea acts as a fuel, add again the 50mL deionized water, constantly stir, boric acid and urea are dissolved fully, obtain clear solution.
(3) drip the dilute nitric acid solution of 2 0.2mol/L in the above-mentioned clear solution, the pH that records solution is 6, stops to drip dilute nitric acid solution, and constantly stirred solution obtains reaction solution.
(4) above-mentioned reaction solution is shifted in heat-resisting crucible, then put in the retort furnace that has been preheating to 700 ℃, under air atmosphere, be incubated 10 minutes and carry out combustion synthesis reaction, be cooled to that room temperature is loosened, the spumescence product, obtain Ca after the grinding
10.32Eu
0.60La
1.08Al
14O
33(referred to as Ca
12Al
14O
33: Eu, La) the light-accumulating luminescent powder.
The XRD figure of products therefrom is seen accompanying drawing 9.Can find out that from accompanying drawing 9 each diffraction peak and standard card JCPDS No.09-0413 meet, show that products therefrom has the crystalline structure of body-centered cubic C 12 A 7, and not have other dephasign to occur.
(5) luminescent properties test
Accompanying drawing 10 is prepared Ca
12Al
14O
33: Eu, the excitation spectrum of La light-accumulating luminescent powder (the monitoring wavelength is 440nm) can be found out from accompanying drawing 10, excitation spectrum is comprised of a Broad excitation band, wavelength region is 280～420nm, excites peak value to be positioned at 335nm, illustrates that ultraviolet ray and purple light can make it effectively be excited and luminous.Accompanying drawing 11 is prepared Ca
12Al
14O
33: Eu, the emmission spectrum of La light-accumulating luminescent powder (usefulness 335nm's is ultraviolet ray excited) can find out that from accompanying drawing 11 its emmission spectrum is wide emission band, and wavelength region is 390～530nm, and luminescence peak is positioned at 440nm, and glow color is indigo.Accompanying drawing 12 is Ca
12Al
14O
33: Eu, the decay of afterglow curve of La light-accumulating luminescent powder.To find out, after-glow brightness decays to 0.32mcd/m from accompanying drawing 12
2The time time of persistence be 50 seconds, show Ca
12Al
14O
33: Eu, La are light-storing and emitting materials.
Claims (3)
1. the preparation method of a rear-earth-doped C 12 A 7 light-accumulating luminescent powder of sending out coloured light indigo is characterized in that this preparation method adopts following steps:
(1) according to chemical general formula Ca
12-x-yAl
14O
33: Eu
x, Re
yMol ratio, be mixed with and contain Ca
2+, Al
3+, Eu
3+, Re
3+The hybrid metal nitrate solution, wherein, Re is any one among Dy, Nd, the La, x=0.06～0.96, y=0.06～1.20;
(2) in above-mentioned hybrid metal nitrate solution, add boric acid or borax as fusing assistant, urea or carbohydrazide act as a fuel, and add deionized water again, constantly stir, and the fusing assistant of adding and fuel are dissolved fully, obtain clear solution;
(3) under the strong stirring, in above-mentioned clear solution, drip dilute nitric acid solution, until the pH of this clear solution till between 5～7, obtains reaction solution;
(4) under air atmosphere, above-mentioned reaction solution was carried out combustion synthesis reaction in 5～10 minutes in 500～750 ℃ of lower insulations, be cooled to that room temperature is loosened, the spumescence product, can obtain light-accumulating luminescent powder of the present invention after the grinding.
2. the preparation method of the rear-earth-doped C 12 A 7 light-accumulating luminescent powder of sending out coloured light indigo as claimed in claim 1 is characterized in that, control adds B behind the described fusing assistant
3+With Al
3+Mol ratio be 5～15%.
3. the preparation method of the rear-earth-doped C 12 A 7 light-accumulating luminescent powder of sending out coloured light indigo as claimed in claim 1 is characterized in that the consumption of described fuel is 4～12 times of described hybrid metal nitrate total mole number.
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