CN104031641B - Fluorescent material based on the aluminate fluorescent powder surface coating method of hydro-thermal reaction and preparation thereof - Google Patents
Fluorescent material based on the aluminate fluorescent powder surface coating method of hydro-thermal reaction and preparation thereof Download PDFInfo
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Abstract
The invention discloses the BaMgAl of a kind of aluminate fluorescent powder surface coating method based on hydro-thermal reaction and preparation thereof10O17: Eu2+MgO fluorescent material, the method first step, combustion method prepares BaMgAl10O17: Eu2+Core, second step, hydro-thermal method cladding MgO film forms nucleocapsid structure, obtains BaMgAl10O17: Eu2+MgO fluorescent material.This nucleocapsid structure aluminate fluorescent powder is by BaMgAl10O17: Eu2+(BAM) Surface coating MgO film realizes, and luminous efficiency and thermal stability are all improved to some extent.The inventive method can prepare the fluorescent material of high brightness, high stability, low surface defect, and this preparation method technique is simple, and synthesis temperature is low, pollution-free, low-cost high-efficiency, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to fluorescent material field, be specifically related to the BaMgAl of a kind of aluminate fluorescent powder surface coating method based on hydro-thermal reaction and preparation thereof10O17: Eu2+MgO fluorescent material.
Background technology
Blue colour fluorescent powder BaMgAl10O17: Eu2+(BAM) because possessing the advantage of high-quantum efficiency and high color purity, and it is widely used in the fields such as fluorescent material, plasma display (PDP) and white light LEDs.Along with the commercialization of BAM, it has been expressed higher great expectations by researcheres, it is proposed that higher requirement.But BAM is in use, owing to VUV excitation radiation and gas discharge ion sputter, it may appear that brightness decay phenomenon.Because the defect that the sputtering of energetic ion can cause fluorescent powder grain surface increases, the surface of crystal is made to be destroyed and then reduce luminous intensity.At present, the performance people in order to improve fluorescent material have attempted various method, for instance doping, adjustment chemical group are graded, but solve problems the best way and be still coated with a tunic layer at phosphor surface.Current conventional high temperature solid-phase sintering method carries out film coated, but it is too high to equipment requirements, wants precise control of temperature during use, causes price and energy consumption higher.
Application publication number is the preparation method that the Chinese invention patent application of CN102337126A (application number is 201110206212.1) discloses a kind of PDP BAM blue colour fluorescent powder, comprises the following steps: 1) by raw material aluminium compound, barium compound, magnesium compound, europium compound according to Ba0.9MgAl10O17: Eu0.1Stoichiometrically ratio carries out dispensing, then to its mixture adding cosolvent and tungsten compound, molybdenum compound or tungsten compound and molybdenum compound, is thoroughly mixed to form compound；2) being loaded by compound in high purity aluminium oxide crucible, in entrance firing furnace, under 1400 DEG C～1500 DEG C nitrogen and hydrogen atmosphere, calcination obtains burned material in 5～10 hours；3) described burned material is pulverized, then sieve, dispersion, cross water sieve, washing, dry, sieve and namely obtain BAM blue colour fluorescent powder；4) the BAM blue colour fluorescent powder of gained is carried out heat treatment in neutral atmosphere or weak oxide atmosphere, sieve after cooling and obtain BAM blue colour fluorescent powder finished product.This technical scheme adopts high temperature solid-phase sintering method, but it is high to equipment requirements, and temperature controls also high, makes energy consumption higher, causes that production cost is higher.
Application number be 201110028392.9 Chinese invention patent application disclose a kind of aluminate blue fluorescent powder and preparation method thereof, including: 2.1 mixing tanks are sequentially added into appropriate alcohol, water and strong aqua ammonia, stirring so that solution mix homogeneously；In above-mentioned solution, slowly drip the mixed liquor of tetraethyl orthosilicate (TEOS), alcohol, continue stirring；2.2 gained solution water bath with thermostatic control 1～10h under 30～80 DEG C of conditions, centrifuge washing, at 80～160 DEG C, dry 12～24h, namely obtains the SiO that size is about 100～1000nm after grinding2Microsphere；2.3 weigh Eu2O3It is dissolved in nitric acid, sequentially adds BaCO3、Mg(NO3)2With Al (NO3)3·9H2O；2.4 add strong aqua ammonia after the heating of above-mentioned mixed solution, magnetic agitation 3～12h, and regulating pH value is 4～8, obtains water white transparency colloidal sol, adds the SiO prepared2Microsphere, stirs 1～12 hour, and solution, at 80～160 DEG C of constant temperature 1～4h, obtains xerogel；Last 800～1000 DEG C of preroasts 2～5 hours, obtain SiO2BaMgAl10O17: Eu2+Nucleocapsid structure.This technical scheme complex process, and the condition of required control is strict, and equipment requirements is higher, and energy consumption is higher, thus causing that the production cost of product is too high.
Summary of the invention
For solving the problems referred to above, the invention provides one and utilize hydro-thermal reaction to realize BaMgAl10O17: Eu2+Phosphor surface cladding method, can efficiently against with solve above-mentioned problems of the prior art, the method pass through hydro-thermal reaction, at BaMgAl prepared by low-temperature combustion method10O17: Eu2+Surface realize the cladding of MgO film, form fluorescent powder with core-shell structure, improve luminescent properties and the emitting performance of fluorescent material, improve the heat stability of fluorescent material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of aluminate fluorescent powder surface coating method based on hydro-thermal reaction, comprises the following steps:
1) it is initially charged europium oxide, magnesium nitrate, barium nitrate, aluminum nitrate, adds boric acid and carbamide, grind and make it be sufficiently mixed to obtain sticky paste；At 500 DEG C～700 DEG C, sticky paste is calcined 0.5～5min, and cooling after insulation, grinding obtain BaMgAl10O17: Eu2+Core；
2) by step 1) obtained BaMgAl10O17: Eu2+Core is put in deionized water, adds solubility magnesium salt, in 150 DEG C～250 DEG C heat treatment 4h-120h after being sufficiently stirred for, finally, cooling, centrifugal, washing, obtain BaMgAl10O17: Eu2+MgO fluorescent material.
Step 1) in, described grinding carries out in agate mortar.
Described calcining includes: first move in crucible by sticky paste, after being warming up to 500 DEG C～700 DEG C in Muffle furnace, is inserted by the crucible filling sticky paste in Muffle furnace and burns, and burning time continues 0.5～5min.
The time of described insulation is 2～10min.
Described europium oxide, magnesium nitrate, barium nitrate, aluminum nitrate addition according to chemical formula BaMgAl10O17: Eu2+Mol ratio calculate obtain.Namely according to chemical formula BaMgAl10O17: Eu2+, described magnesium nitrate, barium nitrate, aluminum nitrate mol ratio be 0.8～1.2:0.8～1.5:10, the addition of described europium oxide is according to Eu2+Required doping content is determined.The mol ratio of described europium oxide and aluminum nitrate is 0.01～0.04:10, suitable Eu2+Doping content is conducive to improving BaMgAl10O17: Eu2+The luminescent properties of MgO fluorescent material.
The mol ratio of described boric acid and aluminum nitrate is 0.03～0.07:10, and the mol ratio of described carbamide and aluminum nitrate is 30～70:10.
Step 2) described in solubility magnesium salt and step 1) in the mol ratio of aluminum nitrate be 5～10:10.
Described solubility magnesium salt is magnesium nitrate.
Described heat treatment carries out in autoclave.
BaMgAl prepared by method of the present invention10O17: Eu2+MgO fluorescent material, by aluminate fluorescent powder BaMgAl10O17: Eu2+Form with MgO, with aluminate fluorescent powder BaMgAl10O17: Eu2+For core, with MgO for shell, namely MgO shell is coated on aluminate fluorescent powder BaMgAl10O17: Eu2+In core.The inventive method prepares BaMgAl10O17: Eu2+Its luminous efficiency of MgO fluorescent material and heat stability all improve.
Compared with prior art, the invention has the beneficial effects as follows:
One, the present invention adopts low-temperature combustion method to prepare BaMgAl10O17: Eu2+Fluorescent material core, MgO is coated on phosphor surface by recycling hydro-thermal method, obtains required nucleocapsid structure aluminate light-emitting particles.This method adopts low-temperature combustion method to prepare the BaMgAl of rare-earth europium doping10O17: Eu2+Fluorescent material, as core, controls BaMgAl10O17: Eu2+Core and MgO shell mol ratio prepare the fluorescent material of high brightness, high stability, low surface defect, and this preparation method technique is simple, and synthesis temperature is low, pollution-free, low-cost high-efficiency, is suitable for large-scale industrialized production, it is easy to accomplish industrialization.
Two, BaMgAl prepared by the inventive method10O17: Eu2+The nucleocapsid structure of MgO fluorescent material is by BaMgAl10O17: Eu2+Surface coating MgO film realizes, and adds MgO and both will not destroy BaMgAl10O17: Eu2+Lattice structure, can reduce again the surface defect of BAM fluorescent material to the utmost, and compared with uncoated BAM fluorescent material, luminous efficiency and thermal stability are all improved to some extent.The MgO film being coated with will not change the lattice structure of fluorescent powder grain, decreases the defect on fluorescent powder grain surface after cladding, makes granule more uniform, and shape is more regular.The BaMgAl of preparation10O17: Eu2+MgO fluorescent material can be applicable to the fields such as PDP display device, white light LEDs.
Accompanying drawing explanation
Fig. 1 is BaMgAl10O17: Eu2+The BAM fluorescent powder grain photoluminescence spectra of MgO fluorescent powder with core-shell structure and uncoated thin film；
Wherein, coatedBaMgAl in Fig. 110O17: Eu2+Refer to BaMgAl10O17: Eu2+MgO fluorescent material, uncoatedBaMgAl10O17: Eu2+Refer to BaMgAl10O17: Eu2+Fluorescent material.
Detailed description of the invention
Embodiment 1:
The first step, combustion method prepares BaMgAl10O17: Eu2+Core, detailed process is as follows: accurately weigh 0.0176gEu2O3, 0.4965gBa (NO3)2, 0.5128gMg (NO3)2·6H2O, 7.5027gAl (NO3)3·9H2O, boric acid 0.006g and carbamide 6g are placed in agate mortar, are fully ground, and make reagent mix homogeneously, obtain sticky paste；Sticky paste being moved into crucible, then is placed in the Muffle furnace of 600 DEG C combustion reaction 1.5min, take out after insulation 5min, cooling is also ground and is obtained BaMgAl10O17: Eu2+Core.
Second step, hydro-thermal method cladding MgO film forms nucleocapsid structure, and detailed process is as follows: the BaMgAl that will obtain10O17: Eu2+Core is dissolved in 100mL deionized water, adds 3.0769gMg (NO3)2·6H2O, is uniformly mixing to obtain mixed solution；Mixed solution is inserted in autoclave, after 150 DEG C of heat treatment 120h, be cooled to room temperature 25 DEG C；Solution after cooling is centrifuged, washs, dries, BaMgAl can be obtained10O17: Eu2+MgO fluorescent powder with core-shell structure.
The BaMgAl that in embodiment 1 prepared by the first step10O17: Eu2+BaMgAl prepared by core (i.e. the BAM fluorescent powder grain of uncoated thin film) and second step10O17: Eu2+The photoluminescence spectra of MgO fluorescent powder with core-shell structure is as shown in Figure 1.As it is shown in figure 1, BaMgAl10O17: Eu2+The luminous efficiency of MgO fluorescent powder with core-shell structure will apparently higher than BaMgAl10O17: Eu2+Core (i.e. the BAM fluorescent powder grain of uncoated thin film), and after lasting 5h, it is always maintained at this trend, it was shown that BaMgAl10O17: Eu2+The thermal stability of MgO fluorescent powder with core-shell structure also will apparently higher than BaMgAl10O17: Eu2+Core (i.e. the BAM fluorescent powder grain of uncoated thin film).
Embodiment 2:
The first step, combustion method prepares BaMgAl10O17: Eu2+Core, detailed process is as follows: accurately weigh 0.0176gEu2O3, 0.4965gBa (NO3)2, 0.5128gMg (NO3)2·6H2O, 7.5027gAl (NO3)3·9H2O, boric acid 0.006g and carbamide 6g are placed in agate mortar, are fully ground, and make reagent mix homogeneously, obtain sticky paste；Sticky paste being moved into crucible, then is placed in the Muffle furnace of 600 DEG C combustion reaction 1min, take out after insulation 5min, cooling is also ground and is obtained BaMgAl10O17: Eu2+Core.
Second step, hydro-thermal method cladding MgO film forms nucleocapsid structure, and detailed process is as follows: the BaMgAl that will obtain10O17: Eu2+Core is dissolved in 100mL deionized water, adds 1.0256gMg (NO3)2·6H2O, is uniformly mixing to obtain mixed solution；Mixed solution is inserted in autoclave, after 180 DEG C of heat treatment 100h, be cooled to room temperature 25 DEG C；Solution after cooling is centrifuged, washs, dries, BaMgAl can be obtained10O17: Eu2+MgO fluorescent powder with core-shell structure.
Embodiment 3:
The first step, combustion method prepares BaMgAl10O17: Eu2+Core, detailed process is as follows: accurately weigh 0.0176gEu2O3, 0.4965gBa (NO3)2, 0.5128gMg (NO3)2·6H2O, 7.5027gAl (NO3)3·9H2O, boric acid 0.006g and carbamide 6g are placed in agate mortar, are fully ground, and make reagent mix homogeneously, obtain sticky paste；Sticky paste being moved into crucible, then is placed in the Muffle furnace of 600 DEG C combustion reaction 2min, take out after insulation 5min, cooling is also ground and is obtained BaMgAl10O17: Eu2+Core.
Second step, hydro-thermal method cladding MgO film forms nucleocapsid structure, and detailed process is as follows: the BaMgAl that will obtain10O17: Eu2+Core is dissolved in 100mL deionized water, adds 0.2564gMg (NO3)2·6H2O, is uniformly mixing to obtain mixed solution；Mixed solution is inserted in autoclave, after 200 DEG C of heat treatment 60h, be cooled to room temperature 25 DEG C；Solution after cooling is centrifuged, washs, dries, BaMgAl can be obtained10O17: Eu2+MgO fluorescent powder with core-shell structure.
Embodiment 4:
The first step, combustion method prepares BaMgAl10O17: Eu2+Core, detailed process is as follows: accurately weigh 0.0176gEu2O3, 0.4965gBa (NO3)2, 0.5128gMg (NO3)2·6H2O, 7.5027gAl (NO3)3·9H2O, boric acid 0.006g and carbamide 6g are placed in agate mortar, are fully ground, and make reagent mix homogeneously, obtain sticky paste；Sticky paste being moved into crucible, then is placed in the Muffle furnace of 600 DEG C combustion reaction 2min, take out after insulation 5min, cooling is also ground and is obtained BaMgAl10O17: Eu2+Core.
Second step, hydro-thermal method cladding MgO film forms nucleocapsid structure, and detailed process is as follows: the BaMgAl that will obtain10O17: Eu2+Core is dissolved in 100mL deionized water, adds 0.1282gMg (NO3)2·6H2O, is uniformly mixing to obtain mixed solution；Mixed solution is inserted in autoclave, after 250 DEG C of heat treatment 4h, be cooled to room temperature 25 DEG C；Solution after cooling is centrifuged, washs, dries, BaMgAl can be obtained10O17: Eu2+MgO fluorescent powder with core-shell structure.
Claims (1)
1. the aluminate fluorescent powder surface coating method based on hydro-thermal reaction, it is characterised in that comprise the following steps:
1) it is initially charged europium oxide, magnesium nitrate, barium nitrate, aluminum nitrate, adds boric acid and carbamide, grind and make it be sufficiently mixed to obtain sticky paste；At 500 DEG C～700 DEG C, sticky paste is calcined 0.5～5min, and cooling after insulation, grinding obtain BaMgAl10O17: Eu2+Core；
Described magnesium nitrate, barium nitrate, aluminum nitrate mol ratio be 0.8～1.2:0.8～1.5:10；
The mol ratio of described europium oxide and aluminum nitrate is 0.01～0.04:10；
Described grinding carries out in agate mortar；
Described calcining includes: first move in crucible by sticky paste, after being warming up to 500 DEG C～700 DEG C in Muffle furnace, is inserted by the crucible filling sticky paste in Muffle furnace and burns, and burning time continues 0.5～5min；
The time of described insulation is 2～10min；
2) by step 1) obtained BaMgAl10O17: Eu2+Core is put in deionized water, adds solubility magnesium salt, described solubility magnesium salt and step 1) in the mol ratio of aluminum nitrate be 5～10:10, in 150 DEG C～250 DEG C heat treatment 4h-120h after being sufficiently stirred for, finally, cooling, centrifugal, washing, obtain BaMgAl10O17: Eu2+MgO fluorescent material, described BaMgAl10O17: Eu2+MgO fluorescent material, by aluminate fluorescent powder BaMgAl10O17: Eu2+Form with MgO, with aluminate fluorescent powder BaMgAl10O17: Eu2+For core, with MgO for shell；
Described solubility magnesium salt is magnesium nitrate.
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| PDP纳米BaMgAl10O17：Eu～（2+）蓝色荧光粉的制备、表面修饰及光谱特性研究;陈哲;《华中科技大学博士学位论文》;20080331;19-20、52、61页 * |
| 纳米复合材料SiC/ZnO、BaMgAl10O17：Eu～（2+）/MgO的制备与性能研究;祝洪洋;《吉林大学硕士学位论文》;20070430;29页4.1 * |
| 纳米复合材料SiC/ZnO、BaMgAl10O17：Eu2+/MgO的制备与性能研究;祝洪洋;《吉林大学硕士学位论文》;20070430;29页4.1 * |
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