CN101497791A - Blue fluorescent powder and preparation thereof - Google Patents

Blue fluorescent powder and preparation thereof Download PDF

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CN101497791A
CN101497791A CNA2009100214391A CN200910021439A CN101497791A CN 101497791 A CN101497791 A CN 101497791A CN A2009100214391 A CNA2009100214391 A CN A2009100214391A CN 200910021439 A CN200910021439 A CN 200910021439A CN 101497791 A CN101497791 A CN 101497791A
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fluorescent powder
blue colour
colour fluorescent
preparation
sintering
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焦桓
马强
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Shaanxi Normal University
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Shaanxi Normal University
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Abstract

A blue-fluorescence powder comprises a material with a general formula of Mg (1-x-y) SryAl2O4: Eux, wherein x is the mole number of europium atom and is less than or equal to 0.005 and more than or equal to 0.10, y is the mole number of strontium atom and is less than or equal to 0.01 and more than or equal to 0.14. A preparation method of the blue-fluorescence powder comprises the following steps of pretreating raw materials, blending, sintering, washing and preparing the blue-fluorescence powder. The blue-fluorescence powder prepared by the preparation method is tested by an X-ray powder diffractometer and a PE spectrofluorimeter and is observed by an environmental scanning electronic microscope, the test and the observation results show that the excitation spectrum of the prepared fluorescence powder adopts a wide band spectrum between 200 nm and 450 nm, the center wavelength of the excitation spectrum is 330 nm, the emission spectrum is a band spectrum positioned between 400 nm and 550 nm under the excitation of 330 nm and 365 nm ultraviolet lights, the center wavelength is 463 nm and is consistent with the spectrum of the common blue fluorescence powder, thereby the fluorescence powder prepared by adopting the preparation method is the blue-fluorescence powder.

Description

Blue colour fluorescent powder and preparation method thereof
Technical field
The invention belongs to the material technology field, be specifically related to blue colour fluorescent powder and preparation method thereof.
Background technology
At present, rare earth luminescent material has become the propping material in fields such as information demonstration, lighting source, photoelectric device, the high luminous intensity of fluorescent material and good microscopic appearance can improve the use properties of device effectively, therefore, the research of novel fluorescent material and application are one of important research field of materials chemistry and materials physics always.The progress of modern science and technology constantly proposes new requirement to luminescent material, because plasma display panel (PDP) has obtained significant improvement at picture quality, resolving power, life-span and power consumption aspects in recent years, plasma display panel (PDP) has come into the market to become one of the strongest rival of large screen display.Plasma display panel (PDP) shows that the molecular formula that adopts is BaMgAl 10O 17: Eu 2+Blue colour fluorescent powder (BAM), in use have the blue colour fluorescent powder aged technical problem be coated on the display panel, cause luminous efficiency and purity of color to descend.
The white light-emitting diode illuminating device has been compared many advantages with the traditional lighting light source,, less energy consumption little as volume, response is fast, the life-span is long, pollution-free etc., therefore be called the 4th generation lighting source.The plurality of advantages of white light-emitting diode has broad application prospects it, is subjected to domestic and international investigator's great attention, but its blue emitting material that is suitable for also preferred in the middle of.It is BaMgAl that three-basic-colour lamp is also selected molecular formula for use 10O 17: Eu 2+Blue colour fluorescent powder (BAM), but in the roasted tube process, have the thermal ageing problem.
In the luminescent device technical field, a current technical problem that presses for solution provides blue colour fluorescent powder of a kind of excellent property and preparation method thereof.
Summary of the invention
A technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned blue colour fluorescent powder, and a kind of luminous intensity height, good stability, blue colour fluorescent powder that purity of color is high are provided.
Another technical problem to be solved by this invention is to provide a kind of preparation method of simple blue colour fluorescent powder.
Solving the problems of the technologies described above the technical scheme that is adopted is to use formula M g 1-x-ySr yAl 2O 4: Eu xThe material of the blue colour fluorescent powder of expression is formed, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14.
Use formula M g 1-x-ySr yAl 2O 4: Eu xThe material of the blue colour fluorescent powder of expression is formed, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, and x the best is 0.02, and y the best is 0.10.
The preparation method of above-mentioned blue colour fluorescent powder is made by following step:
1, the pre-treatment of raw material
With the 850 ℃ of pre-burnings 2 hours in High Temperature Furnaces Heating Apparatus of Strontium carbonate powder and europium sesquioxide, remove wherein moisture and impurity.
2, batching
By formula M g 1-x-ySr yAl 2O 4: Eu xTake by weighing the oxide compound of the oxide compound of the oxide compound of Strontium carbonate powder, magnesium or oxyhydroxide or inorganic salt, aluminium or oxyhydroxide or inorganic salt, europium or nitrate, fusing assistant respectively, in mortar, ground 20 minutes, be prepared into raw mix.
Above-mentioned fusing assistant is a kind of in boric acid, lithium fluoride, barium fluoride, the Quilonum Retard, and the consumption of fusing assistant is 1%～7% of preparation blue colour fluorescent powder quality.
3, sintering
Raw mix being packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, is in the gas mixture of 1:16～99 in the volume ratio of gac or hydrogen and nitrogen, 1300～1500 ℃ of sintering 3～7 hours, and reaction naturally cools to room temperature after finishing.
4, washing
The product of step 3 is put into deionized water be heated to boiling, flush away fusing assistant, repeated washing 2～3 times.
5, preparation blue colour fluorescent powder
Product after the washing was put into 80～100 ℃ of dryings of baking oven 1～2 hour, be ground to 100 order fineness, be prepared into blue colour fluorescent powder with mortar.
In batching step 2 of the present invention, the inorganic salt of raw materials used magnesium are any one in magnesium basic carbonate, Magnesium oxalate (1:1) dihydrate, the magnesium nitrate hexahydrate; The inorganic salt of aluminium are any one in four Aluminum oxalate monohydrates, the ANN aluminium nitrate nonahydrate.In sintering step 3, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, volume ratio at gac or hydrogen and nitrogen is in the gas mixture of 1:16～99, preferred 1350～1450 ℃ of sintering 4～6 hours, reaction naturally cools to room temperature after finishing.
In batching step 2 of the present invention, the optimum amount of fusing assistant is 5% of a prepared blue colour fluorescent powder quality.In sintering step 3 of the present invention, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, be in the gas mixture of 1:16～99 in the volume ratio of gac or hydrogen and nitrogen, preferred 1350 ℃ of sintering 5 hours, reaction naturally cools to room temperature after finishing.
Adopt the blue colour fluorescent powder of the inventive method preparation, with X-ray powder diffraction instrument with the PE fluorescence spectrophotometer is tested and environmental scanning electron microscope is observed, test and observed result show, prepared fluorescent material excitation spectrum is the broadband shape spectrum between 200～450nm, the centre wavelength of excitation spectrum is 330nm, under 330nm and 365nm ultraviolet excitation, its emmission spectrum is the banded spectral line that is positioned at 400～550nm, centre wavelength is 463nm, consistent with the spectrum of conventional blue colour fluorescent powder, illustrate that adopting the prepared fluorescent material of the inventive method is blue colour fluorescent powder.Stereoscan photograph shows that the grain diameter of prepared blue colour fluorescent powder is 2～3 μ m.
Description of drawings
Fig. 1 is the excitation spectrum of the blue colour fluorescent powder of embodiment 1 preparation.
Fig. 2 is that the blue colour fluorescent powder excitation wavelength of embodiment 1 preparation is the emmission spectrum of 254nm.
Fig. 3 is that the blue colour fluorescent powder excitation wavelength of embodiment 1 preparation is the emmission spectrum of 365nm.
Fig. 4 is that the blue colour fluorescent powder excitation wavelength of embodiment 1 preparation is the emmission spectrum of 395nm.
Fig. 5 is the X-ray diffractogram of the blue colour fluorescent powder of embodiment 1 preparation.
Fig. 6 is the stereoscan photograph of the blue colour fluorescent powder of embodiment 1 preparation.
Embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, and x is 0.02, and y is 0.10, and used raw material and preparation method thereof is as follows:
1, raw materials pretreatment
With the 850 ℃ of pre-burnings 2 hours in High Temperature Furnaces Heating Apparatus of Strontium carbonate powder and europium sesquioxide, remove wherein moisture and impurity.
2, batching
By formula M g 0.88Sr 0.10Al 2O 4: Eu 0.02Take by weighing 1.0392g Strontium carbonate powder, 6.0173g magnesium basic carbonate, 10.9824g aluminium hydroxide, 0.2478g europium sesquioxide respectively, fusing assistant is a 0.5g boric acid, grinds 20 minutes in mortar, is prepared into raw mix.
3, sintering
Raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, in gac, 1350 ℃ of sintering 5 hours, reaction naturally cools to room temperature after finishing.
4, washing
The product of step 3 is put into deionized water be heated to boiling, flush away fusing assistant, repeated washing 2～3 times.
5, preparation blue colour fluorescent powder
Product after the washing was put into 80～100 ℃ of dryings of baking oven 1～2 hour, be ground to 100 order fineness, be prepared into blue colour fluorescent powder with mortar.
Embodiment 2
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, and x is 0.02, and y is 0.10, and used raw material and preparation method thereof is as follows:
In batching step 2, by formula M g 0.88Sr 0.10Al 2O 4: Eu 0.02Take by weighing Strontium carbonate powder, magnesium basic carbonate, aluminium hydroxide, europium sesquioxide respectively, consumption is identical with embodiment 1, and fusing assistant is a 0.1g boric acid, and other step of this step is identical with embodiment 1, is prepared into raw mix; In sintering step 3, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, in gac, 1300 ℃ of sintering 7 hours, reaction naturally cools to room temperature after finishing.Other step is identical with embodiment 1, is prepared into blue colour fluorescent powder.
Embodiment 3
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, and x is 0.02, and y is 0.10, and used raw material and preparation method thereof is as follows:
In batching step 2, by formula M g 0.88Sr 0.10Al 2O 4: Eu 0.02Take by weighing Strontium carbonate powder, magnesium basic carbonate, aluminium hydroxide, europium sesquioxide respectively, consumption is identical with embodiment 1, and fusing assistant is a 0.7g boric acid, and other step of this step is identical with embodiment 1, is prepared into raw mix; In sintering step 3, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, in gac, 1500 ℃ of sintering 3 hours, reaction naturally cools to room temperature after finishing.Other step is identical with embodiment 1, is prepared into blue colour fluorescent powder.
Embodiment 4
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, and x is 0.005, and y is 0.14, and used raw material and preparation method thereof is as follows:
In the batching step 2 of above embodiment 1～3, by formula M g 0.855Sr 0.14Al 2O 4: Eu 0.005Take by weighing 1.4549g Strontium carbonate powder, 5.8463g magnesium basic carbonate, 10.9824g aluminium hydroxide, 0.0619g europium sesquioxide respectively, the consumption of fusing assistant boric acid is identical with respective embodiments, grinds 20 minutes in mortar, is prepared into raw mix.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 5
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, and x is 0.10, and y is 0.01, and used raw material and preparation method thereof is as follows:
In the batching step 2 of above embodiment 1～3, by formula M g 0.89Sr 0.01Al 2O 4: Eu 0.10Take by weighing 0.1039g Strontium carbonate powder, 6.0857g magnesium basic carbonate, 10.9824g aluminium hydroxide, 1.2388g europium sesquioxide respectively, the consumption of fusing assistant boric acid is identical with respective embodiments, grinds 20 minutes in mortar, is prepared into raw mix.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 6
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the batching step 2 of above embodiment 1～5, used magnesium basic carbonate is replaced with Magnesium oxalate (1:1) dihydrate, the mole number of magnesium elements is identical, aluminium hydroxide is replaced with aluminum oxide, the mole number of aluminium element is identical, boric acid is replaced with lithium fluoride, and the x in the general formula, the value of y are identical with respective embodiments, and the consumption of lithium fluoride is identical with respective embodiments.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 7
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the batching step 2 of above embodiment 1～5, used magnesium basic carbonate is replaced with magnesium oxide, and the mole number of magnesium elements is identical, and boric acid is replaced with barium fluoride, x in the general formula, the value of y are identical with respective embodiments, and the consumption of barium fluoride is identical with respective embodiments.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 8
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the batching step 2 of above embodiment 1～5, used magnesium basic carbonate is replaced with magnesium nitrate hexahydrate, aluminium hydroxide is replaced with four Aluminum oxalate monohydrates, boric acid is replaced with Quilonum Retard, x in the general formula, the value of y are identical with respective embodiments, and the consumption of Quilonum Retard is identical with respective embodiments.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 9
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the batching step 2 of above embodiment 1～5, used magnesium basic carbonate is replaced with magnesium hydroxide, and the mole number of magnesium elements is identical, and aluminium hydroxide is replaced with ANN aluminium nitrate nonahydrate, and the x in the general formula, the value of y are identical with respective embodiments.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 10
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the sintering step 3 of above embodiment 1～9, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, volume ratio at hydrogen and nitrogen is in the gas mixture of 1:50, sintering temperature is identical with respective embodiments with sintering time, and reaction naturally cools to room temperature after finishing.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 11
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the sintering step 3 of above embodiment 1～9, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, volume ratio at hydrogen and nitrogen is in the gas mixture of 1:16, sintering temperature is identical with respective embodiments with sintering time, and reaction naturally cools to room temperature after finishing.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
Embodiment 12
With preparation formula M g 1-x-ySr yAl 2O 4: Eu xThe blue colour fluorescent powder 10g of expression is an example, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14, and used raw material and preparation method thereof is as follows:
In the sintering step 3 of above embodiment 1～9, raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, volume ratio at hydrogen and nitrogen is in the gas mixture of 1:99, sintering temperature is identical with respective embodiments with sintering time, and reaction naturally cools to room temperature after finishing.Other step is identical with respective embodiments, is prepared into blue colour fluorescent powder.
In order to determine optimised process step of the present invention, the contriver has carried out a large amount of laboratory study tests, and various test situation are as follows:
1, determines Eu 2+Doping
The preparation general formula is Mg 1-x-ySr yAl 2O 4: Eu x(x is the mole number of Eu atom, y is the mole number of strontium atom) every group of blue colour fluorescent powder quality 10g, taking by weighing 8 groups of quality respectively is the 0.7113g Strontium carbonate powder, 10.4394g aluminium hydroxide, 6.1198g, 6.0857g, 6.0515g, 6.0173g, 5.9831g, 5.9489g, 5.9147g, 5.8805g magnesium basic carbonate, 0.0619g, 0.1239g, 0.1858g, 0.2478g, 0.4955g, 0.7433g, 0.9910g, 1.2388g europium sesquioxide, promptly the mole number x of europium atom is respectively 0.005,0.010,0.015,0.020,0.04,0.08,0.10.
In mortar, ground 20 minutes, ground mixture is packed in the corundum crucible, place High Temperature Furnaces Heating Apparatus, 1350 ℃ of sintering are 5 hours in the gac reducing atmosphere, put into deionized water and are heated to boiling, the flush away fusing assistant, repeated washing 2～3 times was put into 80～100 ℃ of dryings of baking oven 1～2 hour, was ground to 100 order fineness with mortar, be prepared into blue colour fluorescent powder, prepared blue colour fluorescent powder is tested its luminous intensity with the PE fluorescence spectrophotometer.
Test result sees Table 1.
Table 1 Eu 2+Doping is to the influence of luminous intensity
Eu 2+Doping (mol) 0.005 0.010 0.015 0.020 0.04 0.06 0.08 0.10
Luminous intensity (a.u.) 648 756 837 945 801 738 639 495
By table 1 as seen, with Eu 2+The variation Mg of doping 1-x-ySr yAl 2O 4: Eu xThe luminous intensity of fluorescent material has obvious variation, Mg 1-x-ySr yAl 2O 4: Eu xThe luminous intensity of fluorescent material is with Eu 2+The increase of doping raises earlier and afterwards reduces, and works as Eu 2+Doping is Mg 1-x-ySr yAl 2O 4: Eu x2% o'clock its luminous intensity of fluorescent material mole number is the highest.It is 0.005～0.10 that the present invention selects the span of the mole number x of europium atom, and wherein x the best is 0.02.
2, determine Sr 2+Doping
The preparation general formula is Mg 1-x-ySr yAl 2O 4: Eu x(x is the mole number of Eu atom, y is the mole number of strontium atom) every group of quality 10g of blue colour fluorescent powder, taking by weighing 14 groups of quality respectively is the 0.2478g europium sesquioxide, 10.4394g aluminium hydroxide, 6.6327g, 6.5643g, 6.4959g, 6.4275g, 6.3592g, 6.2908g, 6.2224g, 6.1540g, 6.0857g, 6.0173g, 5.9489g, 5.8805g, 58121g, 5.7438g magnesium basic carbonate, 0.1039g, 0.2078g, 0.3118g, 0.4157g, 0.5196g, 0.6235g, 0.7275g, 0.9314g, 0.9353g, 1.0392g, 1.1432g, 1.2471g, 1.3510g, 1.4549g Strontium carbonate powder, promptly the mole number y of strontium atom is respectively 0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.10,0.11,0.12,0.13,0.14.Other experimental procedure is identical with experiment 1.Be prepared into 14 groups of blue colour fluorescent powders, test its luminous intensity with the PE fluorescence spectrophotometer.Test result sees Table 2.
Table 2 Sr 2+Doping is to the influence of luminous intensity
Sr 2+Doping (mol 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14
Luminous intensity (a.u.) 297 306 333 342 351 324 261 234 369 918 792 657 603 594
By table 2 as seen, Sr 2+Doping is Mg 1-x-ySr yAl 2O 4: Eu x0.01 of fluorescent material mole number～0.14 o'clock, the luminous intensity of prepared blue colour fluorescent powder is with Sr 2+The increase of doping raises earlier and afterwards reduces Sr 2+Doping is Mg 1-x-ySr yAl 2O 4: Eu x0.10 o'clock of fluorescent material mole number, the luminous intensity of blue colour fluorescent powder is the highest.It is 0.01～0.14 that the present invention selects the span of the mole number y of strontium atom, and wherein y the best is 0.10.
3, determine the kind and the add-on of fusing assistant
(1) determines the kind of fusing assistant
The preparation general formula is Mg 1-x-ySr yAl 2O 4: Eu xEvery group of quality 10g of blue colour fluorescent powder of (x is the mole number of Eu atom, and y is the mole number of strontium atom), the consumption of magnesium basic carbonate, aluminium hydroxide, europium sesquioxide (x is 0.02), Strontium carbonate powder (y is 0.10) is identical with experiment 1.By preparation Mg 1-x-ySr yAl 2O 4: Eu xIt is 0.5g that 5% of quality takes by weighing fusing assistant, and fusing assistant is respectively LiCl, NaCl, KCl, MgCl 2, BaCl 2, LiF, NaF, CaF 2, BaF 2, AlF 3, Li 2CO 3, Na 2CO 3, K 2CO 3, H 3BO 3, (NaPO 3) 6Other experimental procedure is identical with experiment 1.Be prepared into 15 groups of blue colour fluorescent powders, test its luminous intensity with the PE fluorescence spectrophotometer.
Test result sees Table 3.
Table 3 fusing assistant kind is to the influence of luminous intensity
The fusing assistant kind Luminous intensity (a.u.) The fusing assistant kind Luminous intensity (a.u.) The fusing assistant kind Luminous intensity (a.u.)
LiCl 648 LiF 891 Li 2CO 3 783
NaCl 504 NaF 378 Na 2CO 3 513
KCI 549 CaF 2 495 K 2CO 3 477
MgCl 2 459 BaF 2 819 H 3BO 3 907
BaCl 2 522 AlF 3 711 (NaPO 3) 6 441
By table 3 as seen, with the luminous intensity of the variation blue colour fluorescent powder of fusing assistant kind obvious variation is arranged, fusing assistant is LiF, BaF 2, Li 2CO 3, H 3BO 3The time, the luminous intensity of prepared blue colour fluorescent powder is higher.The present invention selects LiF, BaF 2, Li 2CO 3And H 3BO 3The fusing assistant for preparing material as blue colour fluorescent powder.
(2) determine the consumption of fusing assistant
Add LiF and make fusing assistant in the synthesis material of the kind experiment (1) of determining fusing assistant, consumption is respectively 1%, 3%, 4%, 5%, 6%, 7%, 9% of prepared blue colour fluorescent powder quality, and other experimental technique is with to test 1 identical.Be prepared into 7 groups of blue colour fluorescent powders.
The preparation blue colour fluorescent powder that uses the same method adds fusing assistant BaF respectively 2, Li 2CO 3, H 3BO 3In a kind of.Other experimental procedure is identical with experiment 1.Be prepared into 7 groups of blue colour fluorescent powders that adopt different flux.Prepared blue colour fluorescent powder is tested its luminous intensity with the PE fluorescence spectrophotometer, and test result sees Table 4.
Table 4 different flux addition is to the influence of blue colour fluorescent powder luminous intensity
Figure A200910021439D00121
By table 4 as seen, the fusing assistant addition has tangible influence to the luminous intensity of blue colour fluorescent powder, the addition of fusing assistant is 1% of blue colour fluorescent powder quality～7% o'clock, the luminous intensity of prepared blue colour fluorescent powder is higher, wherein the addition of fusing assistant is 5% o'clock of blue colour fluorescent powder quality, and the luminous intensity of blue colour fluorescent powder is the highest.It is 1%～7% of blue colour fluorescent powder quality that the present invention selects the fusing assistant addition, and optimum addition is 5%.
5, sintering temperature is to the influence of blue colour fluorescent powder luminous intensity
The preparation general formula is Mg 1-x-ySr yAl 2O 4: Eu x(x is the mole number of Eu atom, y is the mole number of strontium atom) 6 groups of 10g blue colour fluorescent powders, the consumption of every group of magnesium basic carbonate, aluminium hydroxide is identical with experiment 1, europium sesquioxide (x is 0.02), Strontium carbonate powder (y is 0.10), 5% the boric acid that adds the blue colour fluorescent powder quality respectively is fusing assistant.Volume ratio at hydrogen and nitrogen is in the gas mixture of 1:50, and sintering temperature is respectively 1300,1350,1400,1450,1500 ℃, and sintering time is 5 hours.Other experimental procedure is identical with experiment 1.Be prepared into 6 groups of blue colour fluorescent powders.Test its luminous intensity with the PE fluorescence spectrophotometer.Test result sees Table 5.
Table 5 sintering temperature is to the influence of blue colour fluorescent powder luminous intensity
Sintering temperature (℃) 1300 1350 1400 1450 1500
Luminous intensity (a.u.) 702 912 756 666 585
By table 5 as seen, luminous intensity with the prepared blue colour fluorescent powder of the variation of sintering temperature has obvious variation, and sintering temperature is 1300～1500 ℃, and the luminous intensity of prepared blue colour fluorescent powder is higher, when wherein sintering temperature was 1350 ℃, the luminous intensity of blue colour fluorescent powder was the highest.It is 1300～1500 ℃ that the present invention selects sintering temperature, and optimal sintering temperature is 1350 ℃.
5, sintering time is to the influence of blue colour fluorescent powder luminous intensity
The preparation general formula is Mg 1-x-ySr yAl 2O 4: Eu x5 groups of the 10g blue colour fluorescent powders of (x is the mole number of Eu atom, and y is the mole number of strontium atom), the consumption of every group of magnesium basic carbonate, aluminium hydroxide, europium sesquioxide (x is 0.02), Strontium carbonate powder (y is 0.10) is identical with experiment 1.5% the boric acid that adds the blue colour fluorescent powder quality respectively is fusing assistant.Volume ratio at hydrogen and nitrogen is in the gas mixture of 1:50, and sintering temperature is 1350 ℃, sintering time 3,4,5,6,7 hours respectively.Other experimental procedure is identical with experiment 1.Be prepared into 5 groups of blue colour fluorescent powders.Test its luminous intensity with the PE fluorescence spectrophotometer.Test result sees Table 6.
Table 6 sintering time is to the influence of blue colour fluorescent powder luminous intensity
Sintering time (hour) 3 4 5 6 7
Luminous intensity (a.u.) 477 747 921 630 423
By table 6 as seen, with the variation Mg that burns the time 1-x-ySr yAl 2O 4: Eu xThe luminous intensity of blue colour fluorescent powder has obvious variation, and sintering time is 3～7 hours, and the luminous intensity of prepared blue colour fluorescent powder is higher, and wherein sintering time is 5 hours, and the luminous intensity of blue colour fluorescent powder is the highest.It is 3～7 hours that the present invention selects sintering time, and best sintering time is 5 hours.
In order to verify beneficial effect of the present invention, it is Mg that the contriver adopts the general formula of the embodiment of the invention 1 preparation 1-x-ySr yAl 2O 4: Eu xBlue colour fluorescent powder test, various test case are as follows:
The test article: general formula is Mg 0.88Sr 0.1Al 2O 4: Eu 0.02Blue colour fluorescent powder.
Testing tool: X-ray powder diffraction instrument, model is Rigaku D/max 2550, Japanese Rigalcu company produces; PE fluorescence spectrophotometer, model are Lambd 950, and U.S. Perkin-Elmer company produces; Environmental scanning electron microscope, model Quanta 200, and FEI Co. produces.
The general formula of the embodiment of the invention 1 preparation is Mg 1-x-ySryAl 2O 4: Eu xThe blue colour fluorescent powder material phase analysis adopt X-ray powder diffraction instrument to test by the using method of instrument, test result is seen Fig. 5; UV spectrum is tested by the using method of PE fluorescence spectrophotometer, and test result is seen Fig. 1,2,3,4; The stereoscan photograph of blue colour fluorescent powder is seen Fig. 6.
By Fig. 1,2,3,4 as seen, the excitation spectrum of fluorescent material is the broadband shape spectrum between 200～450nm, and the centre wavelength of excitation spectrum is 330nm, and is consistent with the spectrum of conventional blue colour fluorescent powder.Illustrate that adopting the prepared fluorescent material of the inventive method is blue colour fluorescent powder.
As seen from Figure 5, the position of X-ray diffraction graph and shape show that the blue colour fluorescent powder of preparation has cubic structure.
As seen from Figure 6, stereoscan photograph shows that the grain diameter of prepared blue colour fluorescent powder is 2～3 μ m.

Claims (5)

1, a kind of blue colour fluorescent powder is characterized in that: use formula M g 1-x-ySr yAl 2O 4: Eu xThe material of expression is formed, and x is the mole number of europium atom in the formula, and y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14.
2, according to the described blue colour fluorescent powder of claim 1, it is characterized in that: use formula M g 1-x-ySr yAl 2O 4: Eu xThe material of expression is formed, and wherein the x value is 0.02, and the y value is 0.10.
3, a kind of preparation method of claim 1 blue colour fluorescent powder is characterized in that having following step to make:
(1) raw materials pretreatment
With the 850 ℃ of pre-burnings 2 hours in High Temperature Furnaces Heating Apparatus of Strontium carbonate powder and europium sesquioxide, remove wherein moisture and impurity;
(2) batching
By formula M g 1-x-ySr yAl 2O 4: Eu xTake by weighing the oxide compound of the oxide compound of the oxide compound of Strontium carbonate powder, magnesium or oxyhydroxide or inorganic salt, aluminium or oxyhydroxide or inorganic salt, europium or nitrate, fusing assistant respectively, in mortar, ground 20 minutes, be prepared into raw mix;
Above-mentioned fusing assistant is a kind of in boric acid, lithium fluoride, barium fluoride, the Quilonum Retard, and the consumption of fusing assistant is 1%～7% of preparation blue colour fluorescent powder quality;
(3) sintering
Raw mix being packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, is in the gas mixture of 1:16～99 in the volume ratio of gac or hydrogen and nitrogen, 1300～1500 ℃ of sintering 3～7 hours, and reaction naturally cools to room temperature after finishing;
(4) washing
The product of step (3) is put into deionized water be heated to boiling, flush away fusing assistant, repeated washing 2～3 times;
(5) preparation blue colour fluorescent powder
Product after the washing was put into 80～100 ℃ of dryings of baking oven 1～2 hour, be ground to 100 order fineness, be prepared into blue colour fluorescent powder with mortar.
4, according to the preparation method of the described blue colour fluorescent powder of claim 3, it is characterized in that: in batching step (2), the inorganic salt of raw materials used magnesium are any one in magnesium basic carbonate, Magnesium oxalate (1:1) dihydrate, the magnesium nitrate hexahydrate; The inorganic salt of aluminium are any one in four Aluminum oxalate monohydrates, the ANN aluminium nitrate nonahydrate; In sintering step (3), raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, be in the gas mixture of 1:16～99 in the volume ratio of gac or hydrogen and nitrogen, 1350～1450 ℃ of sintering 4～6 hours, reaction naturally cools to room temperature after finishing.
5, according to the preparation method of the described blue colour fluorescent powder of claim 3, it is characterized in that: in batching step (2), the consumption of fusing assistant is 5% of a prepared blue colour fluorescent powder quality; In sintering step (3), raw mix is packed in the corundum crucible, place in the High Temperature Furnaces Heating Apparatus, be in the gas mixture of 1:50 in the volume ratio of gac or hydrogen and nitrogen, 1350 ℃ of sintering 5 hours, reaction naturally cools to room temperature after finishing.
CNA2009100214391A 2009-03-09 2009-03-09 Blue fluorescent powder and preparation thereof Pending CN101497791A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388081A (en) * 2014-09-28 2015-03-04 东北大学 Synthetic method for aluminate doped with valence-state-controllable rare earth element and product thereof
CN114702955A (en) * 2022-04-07 2022-07-05 旭宇光电（深圳）股份有限公司 Bivalent europium activated cyan fluorescent powder and preparation method and application thereof
CN114874771A (en) * 2022-06-24 2022-08-09 攀枝花学院 All-solid-phase Eu and Dy activated strontium aluminate fluorescent powder and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388081A (en) * 2014-09-28 2015-03-04 东北大学 Synthetic method for aluminate doped with valence-state-controllable rare earth element and product thereof
CN114702955A (en) * 2022-04-07 2022-07-05 旭宇光电（深圳）股份有限公司 Bivalent europium activated cyan fluorescent powder and preparation method and application thereof
CN114702955B (en) * 2022-04-07 2023-12-08 旭宇光电（深圳）股份有限公司 Divalent europium activated cyan fluorescent powder and preparation method and application thereof
CN114874771A (en) * 2022-06-24 2022-08-09 攀枝花学院 All-solid-phase Eu and Dy activated strontium aluminate fluorescent powder and preparation method thereof

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