CN102660267A - Preparation method of aluminate fluorescent powde - Google Patents
Preparation method of aluminate fluorescent powde Download PDFInfo
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- CN102660267A CN102660267A CN2012101146891A CN201210114689A CN102660267A CN 102660267 A CN102660267 A CN 102660267A CN 2012101146891 A CN2012101146891 A CN 2012101146891A CN 201210114689 A CN201210114689 A CN 201210114689A CN 102660267 A CN102660267 A CN 102660267A
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Abstract
本发明公开了一种铝酸盐荧光粉及其制备方法，将含有A源化合物、M源化合物、水合硝酸铝和助熔剂的混合溶液加热搅拌形成胶状体，然后将所述胶状体干燥、高温煅烧，得到化学式为MxAlmOn:Ay的铝酸盐荧光粉。本发明以水合硝酸铝为铝源，由于水合硝酸铝在加热的条件下可以络合氧化物类和卤化物类A源化合物和M源化合物；另一方面，水合硝酸铝溶液呈酸性，对碳酸盐类A源化合物和M源化合物具有溶解分散的作用，从而在水合硝酸铝的络合和溶解效应下，各反应原料得到更均匀的混合，有利于铝酸盐荧光粉发光强度的提高。本发明提供的制备方法工艺简单，无需采用络合剂和沉淀剂等辅助原料，并且制备的铝酸盐荧光粉粒径小而均匀，发光强度较高。
The invention discloses an aluminate fluorescent powder and a preparation method thereof. The mixed solution containing A source compound, M source compound, aluminum nitrate hydrate and flux is heated and stirred to form a colloid, and then the colloid is dried and calcining at a high temperature to obtain an aluminate phosphor with the chemical formula M x Al m O n : A y . The present invention uses hydrated aluminum nitrate as the aluminum source, because hydrated aluminum nitrate can complex oxides and halides A source compounds and M source compounds under heating conditions; The salt A source compound and the M source compound have the effect of dissolving and dispersing, so that under the complexation and dissolution effects of aluminum nitrate hydrate, each reaction raw material is more uniformly mixed, which is beneficial to the improvement of the luminous intensity of the aluminate phosphor. The preparation method provided by the invention has a simple process, does not need to use auxiliary raw materials such as complexing agent and precipitating agent, and the prepared aluminate phosphor has small and uniform particle size and high luminous intensity.
Description
Technical field
The present invention relates to the fluorescent material technical field, more particularly, relate to a kind of preparation method of aluminate fluorescent powder.
Background technology
Photodiode (Light emitting diode; LED) as lighting source compare with the traditional lighting light source have that volume is little, response is fast, the life-span long, less energy consumption and plurality of advantages such as pollution-free; Be called the 4th generation lighting source, be widely used in fields such as LCD backlight, mobile communication, auto lamp, traffic lights, indoor and outdoor lighting.Because photodiode has performance and wide application markets such as considerable energy saving environmental protection, thereby receives extensive concern both domestic and external.
In fields such as LED and display device, the use of aluminate fluorescent powder is the most common.Aluminate fluorescent powder early than 20th century the seventies developed by the people such as Verstegen of Philips, compare with the fluorescent material that uses at that time, it has better optical property and stability, is widely used in fields such as three-color fluorescent lamp.Deepen continuously along with what aluminate fluorescent powder was studied, numerous products constantly are developed out, and aluminate fluorescent powder is being brought into play more and more important effect owing to have high-level efficiency and stability in display devices such as white light LEDs and PDP.
Industry is at present gone up the general using high temperature solid-state method and is produced aluminate fluorescent powder; But; This method needs very high temperature of reaction, causes that the fluorescent material particle diameter is bigger than normal, size-grade distribution is wide, pass through process such as Ball milling and reduce the fluorescent material particle diameter; The fluorescent powder grain surface is damaged, thus each item degradation such as luminosity of the aluminate fluorescent powder that causes preparing.Compare with high temperature solid-state method, liquid phase method is because powder has very high activity, and the temperature of reaction that needs obviously reduces, and need not last handling process such as Ball milling, to a certain degree helps improving each item performance of fluorescent powder grain.Present stage, the liquid phase production method of aluminate fluorescent powder mainly comprised sol-gel method, coprecipitation method and spray pyrolysis etc.But; Above-mentioned liquid phase method has comparison harsh restriction and having relatively high expectations to equipment to the selection of raw material; For example; Need use auxiliary materials such as complexing agent and precipitation agent during the preparation presoma, and the use meeting of above-mentioned auxiliary material influences the luminous intensity of fluorescent material to the stability generation adverse influence of fluorescent material performance.Simultaneously, the liquid phase preparation process process that prior art adopts is difficult to control, complex manufacturing, and production cost is higher, is unfavorable for industrialization production.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of preparation method of aluminate fluorescent powder, and this method technology is simple, need not to adopt auxiliary materials such as complexing agent and precipitation agent, and the aluminate fluorescent powder luminous intensity of preparation is higher.
In order to solve above technical problem, the present invention provides a kind of aluminate fluorescent powder, and chemical formula is suc as formula shown in the I:
M
xAl
mO
n: A
y, formula I
M is one or more among metallic element Y, Ca, Sr, Ba, Na, the Li etc., and A is one or more among REE Eu, Ce, Tb etc. and the Mn, and x, m, n, y are the atomic molar number; 0.7≤x in the formula≤12; 2≤m≤14,4≤n≤33,0.01≤y≤0.3.
Accordingly, the present invention also provides the preparation method of the described aluminate fluorescent powder of a kind of technique scheme, may further comprise the steps:
Step a) will contain the mixing solutions heated and stirred of A source compound, M source compound, nitric hydrate aluminium and fusing assistant, form colloid;
Step b) is dry under 150 ℃～500 ℃ with said colloid, obtains precursor powder after the grinding;
Step c) is carried out high-temperature calcination after said precursor powder is heated up, and obtains aluminate fluorescent powder.
Preferably, said mixing solutions prepares according to following method:
A source compound, M source compound, nitric hydrate aluminium and fusing assistant is soluble in water, obtain mixing solutions.
Preferably, said A source compound be A oxide compound, the carbonate of A or the nitrate salt of A.
Preferably, said M source compound be M oxide compound, the carbonate of M or the halogenide of M.
Preferably, the temperature that heats in the said step a) is 70～90 ℃.
Preferably, said step b) is specially:
Place loft drier or retort furnace in 150 ℃～500 ℃ down dry 3～5h said colloid, obtain precursor powder after the grinding.
Preferably, said step c) is specially:
Step c1) said presoma is placed aluminum oxide, SP 1 or silicon nitride container, tap density is 30～50%;
Step c2) said presoma is carried out high-temperature calcination under 1000～1550 ℃ of temperature.
Preferably, the temperature rise rate of step c) is 4 ℃/min～10 ℃/min.
The present invention provides a kind of aluminate fluorescent powder and preparation method thereof; The mixing solutions heated and stirred that this method will contain A source compound, M source compound, nitric hydrate aluminium and fusing assistant forms colloid; Then that said colloid is dry, high-temperature calcination, obtaining chemical formula is M
xAl
mO
n: A
yAluminate fluorescent powder.Compared with prior art, the present invention is the aluminium source with nitric hydrate aluminium, on the one hand since nitric hydrate aluminium can complexing A source compound under the condition of heating, the M source compound, especially oxide-based and halogenide class A source compound and M source compound; On the other hand; It is acid that the nitric hydrate aluminum solutions is; A source compound and M source compound are had the effect of dissolving dispersive, especially carbonate A source compound and M source compound are had the effect of dissolving dispersive, thereby under the complexing and solubility effect of nitric hydrate aluminium; Each reaction raw materials obtains mixing more uniformly, helps the raising of aluminate fluorescent powder luminous intensity.Secondly, the discharge of gas also helps improving the dispersiveness of precursor powder in the colloid drying step, and then improves each item performance of fluorescent material.Therefore, preparing method's technology provided by the invention is simple, need not to adopt auxiliary materials such as complexing agent and precipitation agent, and the aluminate fluorescent powder particle diameter of preparation is little and even, and luminous intensity is higher.
Description of drawings
Fig. 1 is the XRD figure spectrum of the aluminate fluorescent powder of the embodiment of the invention 1 preparation;
Fig. 2 excites and emmission spectrum figure for the aluminate fluorescent powder of the embodiment of the invention 1 preparation;
Fig. 3 is the XRD figure spectrum of the aluminate fluorescent powder of the embodiment of the invention 2 preparations;
Fig. 4 excites and emmission spectrum figure for the aluminate fluorescent powder of the embodiment of the invention 2 preparation;
Fig. 5 is the XRD figure spectrum of the aluminate fluorescent powder of the embodiment of the invention 3 preparations;
Fig. 6 excites and emmission spectrum figure for the aluminate fluorescent powder of the embodiment of the invention 3 preparation;
Fig. 7 is the XRD figure spectrum of the aluminate fluorescent powder of the embodiment of the invention 4 preparations;
Fig. 8 excites and emmission spectrum figure for the aluminate fluorescent powder of the embodiment of the invention 4 preparation;
Fig. 9 is the XRD figure spectrum of the aluminate fluorescent powder of the embodiment of the invention 5 preparations;
Figure 10 excites and emmission spectrum figure for the aluminate fluorescent powder of the embodiment of the invention 5 preparation;
Figure 11 is the XRD figure spectrum of the aluminate fluorescent powder of the embodiment of the invention 6 preparations;
Figure 12 excites and emmission spectrum figure for the aluminate fluorescent powder of the embodiment of the invention 6 preparation.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of aluminate fluorescent powder, chemical formula is suc as formula shown in the I:
M
xAl
mO
n: A
y, formula I
M is one or more among metallic element Y, Ca, Sr, Ba, Na, the Li etc., and A is one or more among REE Eu, Ce, Tb etc. and the Mn, and x, m, n, y are the atomic molar number; 0.7≤x in the formula≤12; 2≤m≤14,4≤n≤33,0.01≤y≤0.3.
Accordingly; The present invention also provides a kind of preparation method of above-mentioned aluminate fluorescent powder; May further comprise the steps: step a) will contain the mixing solutions heated and stirred of A source compound, M source compound, nitric hydrate aluminium and fusing assistant; Form colloid, M is one or more among metallic element Y, Ca, Sr, Ba, Na, the Li etc., and A is one or more among REE Eu, Ce, Tb etc. and the Mn; Step b) is dry under 150 ℃～500 ℃ with said colloid, obtains precursor powder after the grinding; Step c) is carried out high-temperature calcination after said precursor powder is heated up, and obtains aluminate fluorescent powder.
The present invention does not have special restriction for the preparation method of said mixing solutions, can adopt method well known to those skilled in the art, preferably according to following method preparation: according to M
xAl
mO
n: A
yIn the stoichiometric ratio of each element take by weighing A source compound, M source compound, nitric hydrate aluminium, A source compound, M source compound, nitric hydrate aluminium and fusing assistant is soluble in water, obtain mixing solutions.The activator of elements A for singly mixing or mix altogether among the present invention, the A source compound of employing is preferably the oxide compound of A, the carbonate of A or the nitrate salt of A; The M source compound is preferably the oxide compound of M, the carbonate of M or the halogenide of M.Simultaneously, in order to make each raw material in the mixing solutions more crystalline property is arranged at high temperature, the mixing solutions that the present invention adopts contains fusing assistant.The present invention does not have special restriction for said solubility promoter, is preferably BaF
2Or H
3BO
3
The present invention is the aluminium source with nitric hydrate aluminium, on the one hand, because nitric hydrate aluminium can complex oxide class and halogenide class A source compound and M source compound under the condition of heating; On the other hand; It is acid that the nitric hydrate aluminum solutions is, and carbonate A source compound and M source compound are had the effect of dissolving dispersive, thereby under the complexing and solubility effect of nitric hydrate aluminium; Each reaction raw materials obtains mixing more uniformly, helps the raising of aluminate fluorescent powder luminous intensity.Be preferably the oxide compound of A, the carbonate of A or the nitrate salt of A at the A source compound; When the M source compound is preferably the halogenide of carbonate or M of oxide compound, M of M; Nitric hydrate aluminium has good complexing action to oxide compound and halogenide, can realize oxide compound and the good complexing of halogenide are disperseed; Simultaneously, aluminum nitrate solution is the tart characteristic especially has good dissolving dissemination to the carbonate raw material that looses.
In order to obtain colloid, the present invention carries out heated and stirred to said mixing solutions in step a), preferably utilizes magnetic stirring apparatus, and the temperature of heating is preferably 70～90 ℃, more preferably 75～85 ℃, most preferably is 80 ℃.In the heated and stirred process, the solvent in the mixing solutions constantly evaporates, thereby has formed the heavy-gravity colloid.
After obtaining colloid, comprise also that said step b) is specially and places loft drier or retort furnace in 150 ℃～500 ℃ down dry 3～5h said colloid, obtains precursor powder after the grinding to colloid exsiccant step.In this step, the discharge of gas in the colloid drying process is helped improving the dispersiveness of precursor powder, and then improve each item performance of fluorescent material.
In step c), the present invention carries out high-temperature calcination after said precursor powder is heated up, wherein; Selecting suitable accumulation specific density is one of the important factor of character of the aluminate fluorescent powder of the final preparation of influence, tap density too hour because the contact area between material powder causes the solid phase diffusion distance for a short time; Or do not have suitable way and make the reaction be difficult to carry out fully; May leave in a large number luminescent properties is contributed very little impurity phase, on the other hand, when tap density is too big; Resulting fluorescent material forms hard aggregation easily, reduces the luminous efficiency and the dispersiveness of fluorescent material.This step is selected different atmosphere according to the requirement of variant prodn, like nitrogen atmosphere, and the nitrogen and hydrogen mixture atmosphere, carbon atmosphere or air atmosphere, reducing atmosphere is preferably carried out in nitrogen atmosphere, and oxidizing atmosphere is preferably carried out in air atmosphere; The atmosphere pressures that adopts preferably remains on more than the 1atm.The temperature rise rate of step c) is decided in its sole discretion according to variant prodn, is preferably 4 ℃/min～10 ℃/min, and more preferably 4 ℃/min～6 ℃/min most preferably is 4 ℃/min.Reasonably calcining temperature can suppress the generation of hard aggregation under the prerequisite that crystal grain reaches full growth, and obtains having the aluminate fluorescent powder of the optimum performance of superperformance.Confirm optimum calcinating temperature according to the fluorescent material kind, sintering temperature is too low, and synthetic fluorescent material crystal property is poor, thereby influences luminous intensity; And sintering temperature is too high, and the fluorescent material that obtains forms hard aggregation easily, also can influence luminescent properties.The high-temperature calcination temperature that the present invention adopts is preferably 1000～1550 ℃, more preferably 1000～1500 ℃.
The present invention does not have special restriction for the stove that is used for high-temperature calcination, and the device well known to those skilled in the art that can adopt is preferably the continuous oven or the batch furnace of metallic resistance hot type, graphite resistance hot type or Si-Mo rod resistive heating type.In addition, the present invention also preferably includes the standard of aluminate fluorescent powder being carried out pickling or alkali cleaning, further improves the luminous intensity of the aluminate fluorescent powder of preparation.
In sum, a kind of aluminate fluorescent powder and preparation method thereof being provided, is the aluminium source with nitric hydrate aluminium, on the one hand, because nitric hydrate aluminium can complex oxide class and halogenide class A source compound and M source compound under the condition of heating; On the other hand; It is acid that the nitric hydrate aluminum solutions is, and carbonate A source compound and M source compound are had the effect of dissolving dispersive, thereby under the complexing and solubility effect of nitric hydrate aluminium; Each reaction raw materials obtains mixing more uniformly, helps the raising of aluminate fluorescent powder luminous intensity.Secondly, the discharge of gas in the colloid drying process is also helped improving the dispersiveness of precursor powder, and then improve each item performance of fluorescent material.
Preparing method's technology provided by the invention is simple, need not to adopt auxiliary materials such as complexing agent and precipitation agent, and the aluminate fluorescent powder particle diameter of preparation is little and even, and sintering range is wide, and luminous intensity is higher, has wide prospect in industrial application.Experimental result shows that the particle diameter of the aluminate fluorescent powder of the present invention's preparation is 1 μ m～20 μ m.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment, and employed material, reagent, reducing gas like no specified otherwise, all can obtain from commercial sources.
Embodiment 1
According to chemical formula Y
2.94Ce
0.06Al
5O
12, take by weighing 1.5531gY
2O
3, 8.7755g Al (NO
3)
39H
2O, 0.0483g CeO
2Initial powder adds 0.3g BaF
2As fusing assistant, put into the 100ml beaker jointly, add the zero(ppm) water of 60ml, mixed solution carries out heated and stirred on magnetic stirring apparatus, and Heating temperature remains on 80 ℃, and solvent is constantly evaporated becomes the heavy-gravity colloid until it;
Colloid is put into 300 ℃ of dry 5h of the inherent retort furnace of ceramic boat, and dry back is ground and is obtained presoma;
Presoma is put into the uncovered alumina crucible, and tap density is approximately 30%, puts into alundum furnace; High Temperature Furnaces Heating Apparatus is carried out vacuum pumping; Feed week reduction gas then, promptly in purity is 99.99% nitrogen atmosphere, be raised to 1000 ℃ with 5 ℃/min heat-up rate; Heat-up rate with 4 ℃/min is raised to 1500 ℃ then; Insulation 5h naturally cools to room temperature after being cooled to 800 ℃ with the cooling rate of 4 ℃/min then, puts into after the powder that obtains is taken out and promptly obtains aluminate fluorescent powder after mortar grinds powdered and pickling.
Utilize XRD (X-ray diffractometer) that the phase purity of the aluminate fluorescent powder that obtains is carried out test analysis, the result is as shown in Figure 1.Utilization excites with emmission spectrum the optical property of the fluorescent material that obtains is tested, and the result is as shown in Figure 2, is exciting and emmission spectrum figure of the aluminate fluorescent powder of present embodiment preparation.
Embodiment 2
According to chemical formula Y
2.94Ce
0.06Al
5O
12, take by weighing 1.5531gY
2O
3, 8.7755g Al (NO
3)
39H
2O, 0.1218g Ce (NO
3)
36H
2The initial powder of O adds 0.3g BaF
2As fusing assistant, put into the 100ml beaker jointly, add the zero(ppm) water of 60ml, mixed solution carries out heated and stirred on magnetic stirring apparatus, and Heating temperature remains on 80 ℃, and solvent is constantly evaporated becomes the heavy-gravity colloid until it;
Colloid is put into 300 ℃ of dry 5h of the inherent retort furnace of ceramic boat, and dry back is ground and is obtained presoma;
Presoma is put into the uncovered alumina crucible, and tap density is approximately 30%, puts into alundum furnace; High Temperature Furnaces Heating Apparatus is carried out vacuum pumping; Feed week reduction gas then, promptly in purity is 99.99% nitrogen atmosphere, be raised to 1000 ℃ with 5 ℃/min heat-up rate; Heat-up rate with 4 ℃/min is raised to 1500 ℃ then; Insulation 5h naturally cools to room temperature after being cooled to 800 ℃ with the cooling rate of 4 ℃/min then, puts into after the powder that obtains is taken out and promptly obtains aluminate fluorescent powder after mortar grinds powdered and pickling.
Utilize XRD (X-ray diffractometer) that the phase purity of the aluminate fluorescent powder that obtains is carried out test analysis, the result is as shown in Figure 3.Utilization excites with emmission spectrum the optical property of the fluorescent material that obtains is tested, and the result is as shown in Figure 4, is exciting and emmission spectrum figure of the aluminate fluorescent powder of present embodiment preparation.
Embodiment 3
According to chemical formula Y
2.94Eu
0.06Al
5O
12, take by weighing 1.5531gY
2O
3, 8.7755g Al (NO
3)
39H
2O, 0.0494g Eu
2O
3Initial powder adds 0.3g BaF
2As fusing assistant, put into the 100ml beaker jointly, add the zero(ppm) water of 60ml, mixed solution carries out heated and stirred on magnetic stirring apparatus, and Heating temperature remains on 80 ℃, and solvent is constantly evaporated becomes the heavy-gravity colloid until it;
Colloid is put into 300 ℃ of dry 5h of the inherent retort furnace of ceramic boat, and dry back is ground and is obtained presoma;
Presoma is put into the uncovered alumina crucible, and tap density is approximately 30%, puts into alundum furnace; Then in air atmosphere; Be raised to 1000 ℃ with 5 ℃/min heat-up rate, the heat-up rate with 4 ℃/min is raised to 1500 ℃ then, insulation 5h; Naturally cool to room temperature after being cooled to 800 ℃ with the cooling rate of 4 ℃/min then, put into after the powder that obtains is taken out and promptly obtain aluminate fluorescent powder after mortar grinds powdered and pickling.
Utilize XRD (X-ray diffractometer) that the phase purity of the aluminate fluorescent powder that obtains is carried out test analysis, the result is as shown in Figure 5.Utilization excites with emmission spectrum the optical property of the fluorescent material that obtains is tested, and the result is as shown in Figure 6, is exciting and emmission spectrum figure of the aluminate fluorescent powder of present embodiment preparation.
Embodiment 4
According to chemical formula Ba
0.9Eu
0.1MgAl
10O
17, take by weighing 0.5047g BaCO
3, 0.1145g MgO, 10.6593g Al (NO
3)
39H
2O, 0.0500g Eu
2O
3Initial powder is put into the 100ml beaker jointly, adds the zero(ppm) water of 60ml, and mixed solution carries out heated and stirred on magnetic stirring apparatus, and Heating temperature remains on 80 ℃, and solvent is constantly evaporated becomes the heavy-gravity colloid until it;
Colloid is put into 200 ℃ of dry 4h of the inherent retort furnace of ceramic boat, and dry back is ground and is obtained presoma;
Presoma is put into the uncovered alumina crucible, and tap density is approximately 30%, puts into alundum furnace; High Temperature Furnaces Heating Apparatus is carried out vacuum pumping; Feed week reduction gas then, promptly in purity is 99.99% nitrogen atmosphere, be raised to 1000 ℃ with 5 ℃/min heat-up rate; Heat-up rate with 4 ℃/min is raised to 1550 ℃ then; Insulation 6h naturally cools to room temperature after being cooled to 800 ℃ with the cooling rate of 4 ℃/min then, puts into mortar after the powder that obtains is taken out and grinds powdered and promptly obtain aluminate fluorescent powder.
Utilize XRD (X-ray diffractometer) that the phase purity of the aluminate fluorescent powder that obtains is carried out test analysis, the result is as shown in Figure 7.Utilization excites with emmission spectrum the optical property of the fluorescent material that obtains is tested, and the result is as shown in Figure 8, is exciting and emmission spectrum figure of the aluminate fluorescent powder of present embodiment preparation.
Embodiment 5
According to chemical formula BaAl
11.8Mn
0.2O
19, take by weighing 0.4292g BaCO
3, 9.6273g Al (NO
3)
39H
2O, 0.0500g MnCO
3Initial powder adds 0.2g H
3BO
3As fusing assistant, put into the 100ml beaker jointly, add the zero(ppm) water of 60ml, mixed solution carries out heated and stirred on magnetic stirring apparatus, and Heating temperature remains on 80 ℃, and solvent is constantly evaporated becomes the heavy-gravity colloid until it;
Colloid is put into 200 ℃ of dry 4h of the inherent retort furnace of ceramic boat, and dry back is ground and is obtained presoma;
Presoma is put into the uncovered alumina crucible, and tap density is approximately 30%, puts into alundum furnace; High Temperature Furnaces Heating Apparatus is carried out vacuum pumping; Feed week reduction gas then, promptly in purity is 99.99% nitrogen atmosphere, be raised to 1000 ℃ with 5 ℃/min heat-up rate; Heat-up rate with 4 ℃/min is raised to 1450 ℃ then; Insulation 6h naturally cools to room temperature after being cooled to 800 ℃ with the cooling rate of 4 ℃/min then, puts into mortar after the powder that obtains is taken out and grinds powdered and promptly obtain aluminate fluorescent powder.
Utilize XRD (X-ray diffractometer) that the phase purity of the aluminate fluorescent powder that obtains is carried out test analysis, the result is as shown in Figure 9.Utilization excites with emmission spectrum the optical property of the fluorescent material that obtains is tested, and the result is shown in figure 10, is exciting and emmission spectrum figure of the aluminate fluorescent powder of present embodiment preparation.
Embodiment 6
According to chemical formula Sr
0.99Eu
0.01Al
2O
4, take by weighing 2.9990g SrCl
26H
2O, 8.5275gAl (NO
3)
39H
2O, 0.0200g Eu
2O
3Initial powder is put into the 100ml beaker jointly, adds the zero(ppm) water of 60ml, and mixed solution carries out heated and stirred on magnetic stirring apparatus, and Heating temperature remains on 80 ℃, and solvent is constantly evaporated becomes the heavy-gravity colloid until it;
Colloid is put into 200 ℃ of dry 5h of the inherent retort furnace of ceramic boat, and dry back is ground and is obtained presoma;
Presoma is put into the uncovered alumina crucible, and tap density is approximately 30%, puts into alundum furnace; High Temperature Furnaces Heating Apparatus is carried out vacuum pumping; Feed week reduction gas then, promptly in purity is 99.99% nitrogen atmosphere, be raised to 1000 ℃ with 5 ℃/min heat-up rate; Heat-up rate with 4 ℃/min is raised to 1400 ℃ then; Insulation 4h naturally cools to room temperature after being cooled to 800 ℃ with the cooling rate of 4 ℃/min then, puts into mortar after the powder that obtains is taken out and grinds powdered and promptly obtain aluminate fluorescent powder.
Utilize XRD (X-ray diffractometer) that the phase purity of the aluminate fluorescent powder that obtains is carried out test analysis, the result is shown in figure 11.Utilization excites with emmission spectrum the optical property of the fluorescent material that obtains is tested, and the result is shown in figure 12, is exciting and emmission spectrum figure of the aluminate fluorescent powder of present embodiment preparation.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (9)
1. an aluminate fluorescent powder is characterized in that, chemical formula is suc as formula shown in the I:
M
xAl
mO
n: A
y, formula I
M is one or more among metallic element Y, Ca, Sr, Ba, Na, the Li etc., and A is one or more among REE Eu, Ce, Tb etc. and the Mn, and x, m, n, y are the atomic molar number; 0.7≤x in the formula≤12; 2≤m≤14,4≤n≤33,0.01≤y≤0.3.
2. the preparation method of the described aluminate fluorescent powder of claim 1 is characterized in that, may further comprise the steps:
Step a) will contain the mixing solutions heated and stirred of A source compound, M source compound, nitric hydrate aluminium and fusing assistant, form colloid;
Step b) is dry under 150 ℃～500 ℃ with said colloid, obtains precursor powder after the grinding;
Step c) is carried out high-temperature calcination after said precursor powder is heated up, and obtains aluminate fluorescent powder.
3. preparation method according to claim 2 is characterized in that, said mixing solutions prepares according to following method:
A source compound, M source compound, nitric hydrate aluminium and fusing assistant is soluble in water, obtain mixing solutions.
4. preparation method according to claim 2 is characterized in that, the oxide compound that said A source compound is A, the carbonate of A or the nitrate salt of A.
5. preparation method according to claim 2 is characterized in that, the oxide compound that said M source compound is M, the carbonate of M or the halogenide of M.
6. preparation method according to claim 2 is characterized in that, the temperature that heats in the said step a) is 70～90 ℃.
7. preparation method according to claim 2 is characterized in that, said step b) is specially:
Place loft drier or retort furnace in 150 ℃～500 ℃ down dry 3～5h said colloid, obtain precursor powder after the grinding.
8. preparation method according to claim 2 is characterized in that, said step c) is specially:
Step c1) said presoma is placed aluminum oxide, SP 1 or silicon nitride container, tap density is 30～50%;
Step c2) said presoma is carried out high-temperature calcination under 1000～1550 ℃ of temperature.
9. preparation method according to claim 2 is characterized in that, the temperature rise rate of step c) is 4 ℃/min～10 ℃/min.
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| CN2012101146891A CN102660267A (en) | 2012-04-18 | 2012-04-18 | Preparation method of aluminate fluorescent powde |
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| CN102942930A (en) * | 2012-11-08 | 2013-02-27 | 中国科学技术大学 | Method for preparing high performance aluminate fluorescent powder by pore structure of aluminum oxide |
| CN103710022A (en) * | 2013-11-29 | 2014-04-09 | 佛山安亿纳米材料有限公司 | Light conversion agent, preparation method of light conversion agent, light conversion master batch and preparation method of light conversion master batch |
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| CN102942930A (en) * | 2012-11-08 | 2013-02-27 | 中国科学技术大学 | Method for preparing high performance aluminate fluorescent powder by pore structure of aluminum oxide |
| CN103710022A (en) * | 2013-11-29 | 2014-04-09 | 佛山安亿纳米材料有限公司 | Light conversion agent, preparation method of light conversion agent, light conversion master batch and preparation method of light conversion master batch |
| CN103710022B (en) * | 2013-11-29 | 2016-02-17 | 佛山安亿纳米材料有限公司 | Light-converting agent and preparation method thereof, turn light master batch and preparation method thereof |
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