CN101831293A - Preparation method of blue aluminate fluorescent powder with high brightness and high stability - Google Patents
Preparation method of blue aluminate fluorescent powder with high brightness and high stability Download PDFInfo
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Abstract
The invention relates to a preparation method of blue aluminate fluorescent powder with high brightness and high stability, relating to the preparation of blue aluminate fluorescent powder with a chemical expression of Ba0.9MgAl10O17:0.1Eu2+. The preparation method comprises the following steps of: respectively taking aluminum oxide, aluminum nitride, barium salt, magnesium oxide and europium oxide in a stoichiometric proportion of the fluorescent powder to form a primary raw material; carrying out the ball milling on the primary raw material, a fluxing agent and absolute ethanol or on the primary raw material and the absolute ethanol to obtain raw material powder; calcining the raw material powder in air or in a reduction atmosphere and cooling to a room temperature once or twice to obtain calcined powder; sequentially washing the powder with dilute hydrochloric acid or deionized water at least once; drying to carry out weak ball milling; washing with the deionized water; and drying and sieving to prepare a blue aluminate fluorescent material with high brightness and high stability. The method can prepare the fluorescent powder with even granularity, high brightness and good luminous efficiency and thermal stability.
Description
Technical field
The invention belongs to material manufacturing technology field, relate to a kind of Preparation of Fluorescent Material method that is used for plasma display, be specifically related to a kind of preparation method of blue aluminate fluorescent powder with high brightness and high stability.
Background technology
Than commonly used CRT monitor and LCD display, have the visual angle wide, easily make giant-screen, in light weight, contrast gradient is high, response is fast, colour reproduction is good, undistorted, actual power loss is low and the plasma flat-panel display (PDP) of numerous advantages such as vibration and shock resistant becomes one of present important giant-screen and ultra-thin display mode.The PDP technique of display is a kind of under driving circuit control, the vacuum ultraviolet rays (wavelength is mainly at 147nm and 172nm) that utilizes the basic rare gas mixed gas discharge of xenon (Xe) to produce excites fluorescent material with three basic colour, makes this fluorescent material send a kind of flat panel display of visible light.Circuit and luminescent material are two big key components in the PDP technique of display, perfect day by day along with circuit layout, and the quality of the fluorescent material of selecting for use directly has influence on the whole structure of PDP.Blue powder is mainly europium activated barium Mg aluminate (BAM:Eu) in the PDP fluorescent material with three basic colour at present, and BAM belongs to β-A1
2O
3Structure, divalent europium replaces barium ion and serves as active ions in aluminate, under the vacuum-ultraviolet light irradiation, the matrix absorption vacuum ultraviolet rays is also given divalent europium transmission ofenergy, the electronics of europium ion is in the higher excitation level, to minimum excited level, last electronics transits to ground state emission blue light from minimum excited level to electronics by radiationless relaxation then.BAM has emissive porwer preferably, but in roasting screen technological process, because β-Al
2O
3The defective of structure, and Eu
2+Oxidized, make the tristimulus coordinates of fluorescent material be offset, and cause serious light decay.Studies show that the thermal degradation when of BAM mainly is because the instability of specular layer causes, and specular layer is carried out the thermostability that modification can significantly improve BAM.Patent " vacuum ultraviolet rays activated blue aluminate fluorescent powder preparation method " (patent No. 02155321.1, publication number CN141569A, open day 2003.05.07) discloses a kind of blue colour fluorescent powder Ba
1-xEu
xMgAl
10O
17The preparation method, in preparation process, need the material of finishing calcination is carried out ball milling, and the rubbing effect that rolls in the mechanical milling process makes and produces lattice defect in the crystal grain, become the radiationless transition center, also may produce unbodied not light-emitting film at plane of crystal, the brightness of grievous injury fluorescent material and luminous efficiency, therefore, this method can not well satisfy the demand of actual production.
Summary of the invention
In order to overcome above-mentioned problems of the prior art, the preparation method who the purpose of this invention is to provide a kind of blue aluminate fluorescent powder with high brightness and high stability, only need the material of finishing calcination is carried out the weak ball milling of a short period, avoid lattice defect that produces because of ball milling and the amorphous not light-emitting film that produces at plane of crystal, improved the brightness and the luminous efficiency of fluorescent material.
For achieving the above object, the technical solution adopted in the present invention is, a kind of preparation method of blue aluminate fluorescent powder with high brightness and high stability, and relating to chemical expression is Ba
0.9MgAl
10O
17: 0.1Eu
2+The preparation of blue aluminate fluorescent powder, this method is carried out according to the following steps:
Step 1: by the stoichiometric ratio of above-mentioned fluorescent material chemical expression, get aluminum oxide, aluminium nitride, barium salt, magnesium oxide and europium sesquioxide respectively, form starting raw material,
Get fusing assistant,
In the ratio that adds 100ml～150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol,
Above-mentioned starting raw material, fusing assistant and dehydrated alcohol are mixed, and ball milling 10 hours～24 hours obtains raw material powder;
Perhaps, stoichiometric ratio by above-mentioned fluorescent material is got aluminum oxide, aluminium nitride, barium salt, magnesium oxide and europium sesquioxide respectively, form starting raw material, again in the ratio that adds 100ml～150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, with starting raw material and dehydrated alcohol ball milling 10 hours～24 hours, obtain raw material powder;
Step 2: the raw material powder that step 1 is obtained places the environment of bubbling air or reducing atmosphere, temperature rise rate with 5 ℃/min～10 ℃/min, envrionment temperature is risen to 1100 ℃～1700 ℃, be incubated 2 hours～10 hours, then, be cooled to room temperature, this process is carried out once or twice, obtains the powder after the roasting;
Step 3: with the powder after the roasting in the step 2, under condition of stirring, put into dilute hydrochloric acid successively and deionized water washs once at least, oven dry;
Step 4: with ball milling a little less than the powder after step 3 oven dry 1 time～2 times, and use deionized water wash, after the oven dry, sieve, make the blue aluminate fluorescent material of high brightness and high stability.
Barium salt in the described step 1 adopts barium sulfate or barium carbonate.
Fusing assistant in the described step 1 adopts a kind of in bicarbonate of ammonia, aluminum fluoride, Quilonum Retard or the boric acid, perhaps two kinds combination, when the fusing assistant that adopts is a kind of material, the quality of this fusing assistant is 2%～6% of a starting raw material quality, when the fusing assistant that adopts is the combination of two kinds of materials, the quality of this fusing assistant is 1～10% of a starting raw material quality, and to form between two kinds of materials of this fusing assistant be arbitrary proportion.
The mixed gas that reducing atmosphere in the described step 2 adopts per-cent by volume to be made up of the hydrogen of 90%～95% nitrogen and 5%～10%.
The temperature of dilute hydrochloric acid and deionized water is 60 ℃～70 ℃ in the described step 3.
The rotating speed that weak ball milling adopts in the described step 4 is 10 commentaries on classics/min～30 commentaries on classics/min, and the time is 30 minutes～60 minutes.
Order number when sieving in the described step 4 is 1250 orders～2500 orders.
Preparation method of the present invention adopts non-toxic material as raw material, the material of finishing calcination is carried out ball milling a little less than the short period of time, avoided material production lattice defect and plane of crystal to produce unbodied not light-emitting film, brightness, luminous efficiency and the thermostability of fluorescent material have been improved effectively, and the epigranular of the fluorescent material of making is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM figure that adopts the inventive method synthetic blue aluminate fluorescent powder.
Fig. 2 adopts the inventive method blue aluminate fluorescent powder that makes and the emmission spectrum comparison diagram of blue aluminate fluorescent powder thermal treatment front and back under wavelength 147nm vacuum ultraviolet rays excites that adopts traditional method to make.Among the figure, A represents the preceding spectral radiation curves of blue aluminate fluorescent powder thermal treatment that embodiment 14 makes, B represents the preceding spectral radiation curves of blue aluminate fluorescent powder thermal treatment that Comparative Examples 2 makes, C represents the spectral radiation curves after the blue aluminate fluorescent powder thermal treatment that embodiment 14 makes, and D represents the spectral radiation curves after the blue aluminate fluorescent powder thermal treatment that Comparative Examples 24 makes.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
The chemical expression of the blue aluminate fluorescent powder that the present invention relates to is: Ba
0.9MgAl
10O
17: 0.1Eu
2+This fluorescent material prepares by following steps:
Step 1: by the stoichiometric ratio of above-mentioned fluorescent material chemical expression, get aluminum oxide, aluminium nitride, barium salt, magnesium oxide and europium sesquioxide respectively, form starting raw material, then, get fusing assistant, again in the ratio that adds 100～150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol
Starting raw material, fusing assistant and dehydrated alcohol are mixed, and ball milling 10～24 hours obtains raw material powder, and the medium particle diameter of this raw material powder is 0.9～2.1 μ m;
Perhaps, get aluminum oxide, aluminium nitride, barium salt, magnesium oxide and europium sesquioxide respectively by the stoichiometric ratio that above-mentioned fluorescent material is formed, form starting raw material, again in the ratio that adds 100～150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, with starting raw material and dehydrated alcohol ball milling 10～24 hours, obtain raw material powder, the medium particle diameter of this raw material powder is 0.25um;
Barium salt adopts barium sulfate or barium carbonate.
Fusing assistant adopts a kind of in bicarbonate of ammonia, aluminum fluoride, Quilonum Retard or the boric acid, perhaps two kinds combination.When the fusing assistant that adopts is a kind of material, the quality of this fusing assistant is 2～6% of a starting raw material quality, when the fusing assistant that adopts was the combination of two kinds of materials, the quality of this fusing assistant was 1～10% of a starting raw material quality, and to form between two kinds of materials of this fusing assistant be arbitrary proportion.
Step 2: the raw material powder that step 1 is obtained places the environment of bubbling air or reducing atmosphere, with the temperature rise rate of 5～10 ℃/min, envrionment temperature is risen to 1100～1700 ℃, be incubated 2～10 hours, then, be cooled to room temperature, this process is carried out once or twice, obtains the powder after the roasting;
Reducing atmosphere adopts by volume per-cent by 90～95%N
2With 5～10%H
2The mixed gas of forming.
Step 3: the powder after the roasting that step 2 is obtained, adopt following method to wash at least once under condition of stirring: the dilute hydrochloric acid of putting into temperature earlier and be 60～70 ℃ washs, and the deionized water of putting into temperature then and be 60～70 ℃ washs oven dry afterwards;
Step 4: with ball milling a little less than the powder after step 3 oven dry 1～2 time, and use deionized water wash, dry again,, make the blue aluminate fluorescent material of high brightness and high stability with 1250 orders～2500 purpose sieve.
The rotating speed that weak ball milling adopts is 10～30 commentaries on classics/min, and the time is 30～60 minutes.
Adopt the inventive method preparation to be used for the blue aluminate fluorescent powder of plasma display, raw material through after the roasting, is carried out weak ball milling and obtains required fluorescent material.The poor stability of europium activated barium Mg aluminate (BAM) is because the specular layer instability causes.In system screen technology, need in bake process, form a large amount of oxygen rooms through one 500～600 ℃ aerobic bake process at phosphor surface, make divalent europium enter into spinel layer by the oxygen room, cause the colourity drift of fluorescent material; Sauerstoffatom enters into lattice by specular layer and makes divalent europium be oxidized to trivalent europium ion in addition, makes the luminosity of fluorescent material reduce.The inventive method is chosen barium sulfate and aluminium nitride as raw material, is exactly to introduce nitrogen element and element sulphur in specular layer, in order to replace oxygen element.Because nitrogen ionic radius and sulfonium ion radius are all big than oxonium ion radius, can effectively stop the formation in oxygen room and moving of europium ion, make fluorescent material colourity bigger skew can not take place; In addition, the electronegativity of nitrogen and the electronegativity of sulphur are littler than the electronegativity of oxygen, can stablize the not oxidized one-tenth trivalent europium ion of divalent europium, thereby reach the effect that improves the fluorescent material thermostability.Simultaneously, because the rubbing effect that rolls in the mechanical milling process makes and produces lattice defect in the crystal grain, become the radiationless transition center, also may on plane of crystal, produce unbodied not light-emitting film, this is with the brightness and the luminous efficiency of grievous injury fluorescent material, so in the inventive method, the powder after the roasting is carried out weak ball milling, crystal formation to fluorescent material can not cause very big influence, to keep the brightness and the luminous efficiency of fluorescent material.
The blue aluminate fluorescent powder that adopts present method to make has brightness height, thermostability and characteristics such as good dispersity and uniform particles, is easy to realize scale operation, can be used in demonstration such as plasma panel display, rare gas lamp and the illuminating device.
Embodiment 1
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+Stoichiometric ratio by this chemical formula is got aluminum oxide, aluminium nitride, barium sulfate, magnesium oxide and europium sesquioxide respectively, form starting raw material, get bicarbonate of ammonia by 2% of starting raw material quality, in the ratio that adds the 100ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, starting raw material, bicarbonate of ammonia and dehydrated alcohol were mixed the back ball milling 10 hours, obtain the raw material powder that medium particle diameter is 0.9～2.1 μ m; This raw material powder is placed the environment of bubbling air,, envrionment temperature is risen to 1100 ℃, be incubated 10 hours, be cooled to room temperature, obtain the powder after the roasting with the temperature rise rate of 5 ℃/min; With the powder after this roasting, the dilute hydrochloric acid of putting into temperature earlier and be 60 ℃ under condition of stirring washs, and then to put into temperature be that 60 ℃ deionized water washs the oven dry of washing back; With ball milling 1 time a little less than the powder after the oven dry, weak rotational speed of ball-mill is 10 commentaries on classics/min, and the time is 60 minutes, and uses deionized water wash, after the oven dry, with 1250 purpose sieve, makes the blue aluminate fluorescent material of high brightness and high stability.
Embodiment 2
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+Stoichiometric ratio by this chemical formula is got aluminum oxide, aluminium nitride, barium carbonate, magnesium oxide and europium sesquioxide respectively, form starting raw material, get aluminum fluoride by 6% of this starting raw material quality, again in the ratio that adds the 150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, starting raw material, aluminum fluoride and dehydrated alcohol were mixed the back ball milling 24 hours, obtain the raw material powder that medium particle diameter is 0.9～2.1 μ m; This raw material powder is placed the environment that feeds reducing atmosphere, and this reducing atmosphere by volume per-cent is made up of 90% nitrogen and 10% hydrogen; With the temperature rise rate of 10 ℃/min, envrionment temperature is risen to 1700 ℃, be incubated 2 hours, then, be cooled to room temperature, this process carries out twice, obtains the powder after the roasting; With the powder after this roasting, the dilute hydrochloric acid of putting into temperature earlier and be 70 ℃ under condition of stirring washs, and the deionized water of putting into temperature again and be 65 ℃ washs the oven dry of washing back; With the powder after the oven dry is weak ball milling 30 minutes under the condition of 30 commentariess on classics/min at rotating speed, carry out 2 times altogether a little less than ball milling, then, after drying with deionized water wash,, make the blue aluminate fluorescent material of high brightness and high stability with 2500 purpose sieve.
Embodiment 3
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+Stoichiometric ratio by this chemical formula is got aluminum oxide, aluminium nitride, barium carbonate, magnesium oxide and europium sesquioxide respectively, form starting raw material, get Quilonum Retard by 4% of this starting raw material quality, in the ratio that adds the 125ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol again, starting raw material, Quilonum Retard and dehydrated alcohol are mixed, ball milling 17 hours obtains the raw material powder that medium particle diameter is 0.9～2.1 μ m; This raw material powder is placed the environment that feeds reducing atmosphere, and this reducing atmosphere by volume per-cent is made up of 95% nitrogen and 5% hydrogen; With the temperature rise rate of 7.5 ℃/min, this envrionment temperature is risen to 1400 ℃, be incubated 6 hours, be cooled to room temperature, obtain the powder after the roasting; With the powder after this roasting, the dilute hydrochloric acid of putting into temperature earlier and be 65 ℃ under condition of stirring washs, and the deionized water of putting into temperature again and be 70 ℃ washs the oven dry of washing back; With the powder after the oven dry is under the condition of 20 commentaries on classics/min at rotating speed, and weak ball milling 45 minutes is used deionized water wash then, after the oven dry, with 1800 purpose sieve, makes the blue aluminate fluorescent material of high brightness and high stability.
Embodiment 4
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+, get aluminum oxide, aluminium nitride, barium sulfate, magnesium oxide and europium sesquioxide respectively by the stoichiometric ratio of this chemical formula, form starting raw material.Get bicarbonate of ammonia and boric acid respectively by arbitrary proportion, mix and form fusing assistant, then, get this fusing assistant by 1% of starting raw material quality, in the ratio that adds the 110ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol again, starting raw material, fusing assistant and dehydrated alcohol are mixed, ball milling 11 hours obtains the raw material powder that medium particle diameter is 0.9～2.1 μ m; This raw material powder is placed the environment that feeds reducing atmosphere, and this reducing atmosphere by volume per-cent is made up of 92.5% nitrogen and 7.5% hydrogen; With the temperature rise rate of 6 ℃/min, this envrionment temperature is risen to 1200 ℃, be incubated 8 hours, be cooled to room temperature, this process carries out twice, obtains the powder after the roasting; With the powder after the roasting, the dilute hydrochloric acid of putting into temperature earlier and be 62 ℃ under condition of stirring washs, and the deionized water of putting into temperature again and be 69 ℃ washs the oven dry of washing back; With the powder after the oven dry is under the condition of 15 commentaries on classics/min at rotating speed, weak ball milling 52 minutes, and the down weak ball milling of the same terms 2 times is used deionized water wash then, after the oven dry, with 1300 purpose sieve, makes the blue aluminate fluorescent material of high brightness and high stability.
Embodiment 5
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+, get aluminum oxide, aluminium nitride, barium sulfate, magnesium oxide and europium sesquioxide respectively by the stoichiometric ratio of this chemical formula, form starting raw material.Get Quilonum Retard and boric acid respectively by arbitrary proportion, mix to form and get fusing assistant, get this fusing assistant by 10% of starting raw material quality, again in the ratio that adds the 140ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, starting raw material, fusing assistant and dehydrated alcohol are mixed, and ball milling 23 hours obtains the raw material powder that medium particle diameter is 0.9～2.1 μ m; This raw material powder is placed the environment of bubbling air,, envrionment temperature is risen to 1600 ℃, be incubated 5 hours, be cooled to room temperature, obtain the powder after the roasting with the temperature rise rate of 9 ℃/min; With the powder after the roasting, the dilute hydrochloric acid of putting into temperature earlier and be 68 ℃ under condition of stirring washs, and the deionized water of putting into temperature again and be 62 ℃ washs the oven dry of washing back; With the powder after the oven dry is under the condition of 25 commentaries on classics/min at rotating speed, weak ball milling 38 minutes; Use deionized water wash then, after the oven dry,, make the blue aluminate fluorescent material of high brightness and high stability with 2000 purpose sieve.
Embodiment 6
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+, get aluminum oxide, aluminium nitride, barium carbonate, magnesium oxide and europium sesquioxide respectively by the stoichiometric ratio of this chemical formula, form starting raw material.Get aluminum fluoride and Quilonum Retard respectively by arbitrary proportion, mix and form fusing assistant, ratio in starting raw material quality 6%, get this fusing assistant, in the ratio that adds the 130ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol again, starting raw material, fusing assistant and dehydrated alcohol are mixed, ball milling 20 hours obtains the raw material powder that medium particle diameter is 0.9～2.1 μ m; This raw material powder is placed the environment that feeds reducing atmosphere, and this reducing atmosphere by volume per-cent is made up of 91% nitrogen and 9% hydrogen.With the temperature rise rate of 8 ℃/min, envrionment temperature is risen to 1300 ℃, be incubated 7 hours, be cooled to room temperature, this roasting process carries out twice, obtains the powder after the roasting; With the powder after the roasting, the dilute hydrochloric acid of putting into temperature earlier and be 64 ℃ under condition of stirring washs, and the deionized water of putting into temperature again and be 67 ℃ washs the oven dry of washing back; With the powder after the oven dry is under the condition of 12 commentariess on classics/min at rotating speed, weak ball milling 55 minutes, and ball milling 2 times a little less than under identical condition, use deionized water wash then, after the oven dry,, make the blue aluminate fluorescent material of high brightness and high stability with 2400 purpose sieve.
Embodiment 7
Chemical expression Ba according to blue aluminate fluorescent powder
0.9MgAl
10O
17: 0.1Eu
2+, get aluminum oxide, aluminium nitride, barium carbonate, magnesium oxide and europium sesquioxide respectively by the stoichiometric ratio of this chemical formula, form starting raw material.In the ratio that adds the 120ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, with starting raw material and dehydrated alcohol ball milling 15 hours, obtain the raw material powder that medium particle diameter is 0.25 μ m; This raw material powder is placed the environment that feeds reducing atmosphere, and this reducing atmosphere by volume per-cent is made up of 94% nitrogen and 6% hydrogen; With the temperature rise rate of 5 ℃/min, envrionment temperature is risen to 1500 ℃, be incubated 5.5 hours, be cooled to room temperature, this roasting process carries out twice, obtains the powder after the roasting; With the powder after the roasting, under condition of stirring, successively put into temperature and be the deionized water that 70 ℃ dilute hydrochloric acid and temperature be 70 ℃ and wash the oven dry of washing back; With the powder after the oven dry is under the condition of 28 commentariess on classics/min at rotating speed, and weak ball milling 32 minutes is used deionized water wash then, dries, and with 1600 purpose sieve, makes the blue aluminate fluorescent material of high brightness and high stability.
Embodiment 8
Prepare the blue aluminate fluorescent material of high brightness and high stability by the method for embodiment 1, fusing assistant used in the preparation process is made up of the bicarbonate of ammonia and the aluminum fluoride of arbitrary proportion.
Embodiment 9
Prepare the blue aluminate fluorescent material of high brightness and high stability by the method for embodiment 2, fusing assistant used in the preparation process is made up of the bicarbonate of ammonia and the Quilonum Retard of arbitrary proportion.
Embodiment 10
Prepare the blue aluminate fluorescent material of high brightness and high stability by the method for embodiment 3, fusing assistant used in the preparation process is made up of the aluminum fluoride and the boric acid of arbitrary proportion.
Embodiment 11
Prepare the blue aluminate fluorescent material of high brightness and high stability by the method for embodiment 4, used fusing assistant is a boric acid in the preparation process.
Embodiment 12
Take by weighing BaCO
3(AR) 1.7760g (0.009mol), MgO (AR) 0.4030g (0.01mol), Al
2O
3(AR) 5.0850g (0.0499mol), Eu
2O
3(99.99%) 0.1760g (0.05mol), AlN (99.99%) 0.012g (0.03mol) forms starting raw material, adds the NH of 0.2608g (3.5wt%) in this starting raw material respectively
4HCO
3(AR) and the AlF (AR) of 0.2608g (3.5wt%) as fusing assistant, the dehydrated alcohol that adds 120ml again, ball milling 10 hours, obtain raw material powder, this raw material powder is placed the environment of the reducing atmosphere that feeding is made up of 95%N2 and 5%H2 by volume, envrionment temperature is risen to 1500 ℃ of calcinations 4 hours, be cooled to room temperature with the temperature rise rate of 10 ℃/min, burnt powder is successively washed in the deionized water of 60 ℃ dilute hydrochloric acid and 60 ℃, stir simultaneously; Carry out weak ball milling after the oven dry, the powder behind the weak ball milling is used deionized water wash again, 1250 mesh sieves are crossed in the oven dry back, make blue aluminate fluorescent powder with high brightness and high stability.After testing, the medium particle diameter of this fluorescent material is 3.9 μ m, and the luminosity under wavelength 147nm vacuum ultraviolet rays excites is 106, and it is that its luminosity was 94 after 500 ℃ air was handled 2h that this fluorescent material is placed temperature.
Embodiment 13
Take by weighing BaSO
4(AR) 2.1010g (0.009mol), MgO (AR) 0.4030g (0.01mol), Al
2O
3(AR) 5.0980g (0.05mol), Eu
2O
3(99.99%) 0.1760g (0.05mol) forms starting raw material, adds the LiCO of 0.2608g (3.5wt%) in this starting raw material respectively
3(AR) and the H of 0.2608g (3.5wt%)
3BO
3(AR) as fusing assistant, other conditions are with embodiment 12, make the blue aluminate fluorescent powder of high brightness and high stability, after testing, the medium particle diameter of this fluorescent material is 4.1 μ m, luminosity under wavelength excites for the 147nm vacuum ultraviolet rays is 104, and it is that its luminosity was 93 after 500 ℃ air was handled 2h that this fluorescent material is placed temperature.
Embodiment 14
Take by weighing BaCO
3(AR) 1.7760g (0.009mol), MgO (AR) 0.4030g (0.01mol), Al
2O
3(AR) 5.0850g (0.0499mol), Eu
2O
3(99.99%) 0.1760g (0.05mol), AlN (99.99%) 0.012g (0.03mol) forms starting raw material, the dehydrated alcohol that in this starting raw material, adds 120ml, ball milling 10 hours obtains raw material powder, places feeding by volume by 95%N this raw material powder
2And 5%H
2In the environment of the reducing atmosphere of forming, temperature rise rate with 10 ℃/min is warming up to 1450 ℃, calcination 3 hours, cooling is taken out, and the temperature rise rate with 15 ℃/min is warming up to 1200 ℃ again, calcination 2 hours, it is that 60 ℃ dilute hydrochloric acid temperature is that 60 ℃ deionized water washs that powder after the calcination is successively put into temperature, the weak ball milling 0.5h in oven dry back crosses 2500 mesh sieves, makes blue aluminate fluorescent powder with high brightness and high stability.The system sample shown in figure one, as can be seen, sample dispersion is good, is similar to the class sphere.After testing, the medium particle diameter of this fluorescent material is 4.8 μ m, and the luminosity under wavelength 147nm vacuum ultraviolet rays excites is 108, and after handling 2h under 500 ℃ the temperature, its luminosity is 98 with this fluorescent material.
Comparative Examples 1
Take by weighing BaCO
3(AR) 1.7760g (0.009mol), MgO (AR) 0.4030g (0.01mol), Al
2O
3(AR) 5.0980g (0.05mol), Eu
2O
3(99.99%) 0.176g (0.05mol) forms starting raw material, adds the LiCO of 0.2608g (3.5wt%) in this starting raw material respectively
3(AR) and AlF (AR) 0.2608g (3.5wt%) of 0.2608g (3.5wt%) as fusing assistant, add the dehydrated alcohol of 120ml again, ball milling 10 hours obtains raw material powder, places feeding by volume by 95%N this raw material powder
2And 5%H
2In the environment of the reducing atmosphere of forming, temperature rise rate with 10 ℃/min rises to 1500 ℃ of calcinations 4 hours with envrionment temperature, be cooled to room temperature, it is the deionized water washed twice that 70 ℃ dilute hydrochloric acid and temperature are 65 ℃ that burnt powder is successively put into temperature, stirs in the time of washing; Carry out weak ball milling after the oven dry, powder behind the weak ball milling is used deionized water wash again, the oven dry back is crossed 1250 order mesh sieves and is made blue aluminate fluorescent powder, after testing, the medium particle diameter of this fluorescent material is 3.8 μ m, luminosity under wavelength 147nm vacuum ultraviolet rays excites is 102, and after handling 2h under 500 ℃ the temperature, its luminosity is 90 with this fluorescent material.
Comparative Examples 2
Take by weighing BaCO
3(AR) 1.7760g (0.009mol), MgO (AR) 0.4030g (0.01mol), Al
2O
3(AR) 5.0980g (0.05mol), Eu
2O
3(99.99%) 0.176g (0.05mol) forms starting raw material, adds the 120ml dehydrated alcohol in this starting raw material, and ball milling 10 hours obtains raw material powder, places feeding by volume by 95%N this raw material powder
2And 5%H
2In the environment of the reducing atmosphere of forming, temperature rise rate with 10 ℃/min rises to 1700 ℃ of calcinations 4 hours with envrionment temperature, be cooled to room temperature, it is the deionized water washed twice that 60 ℃ dilute hydrochloric acid and temperature are 70 ℃ that the sample that calcining is obtained is successively put into temperature, stirs in the time of washing; Carry out ball milling after the oven dry, the sample behind the ball milling is used deionized water wash again, 2500 order mesh sieves are crossed in the oven dry back, make blue aluminate fluorescent powder.After testing, the medium particle diameter of this fluorescent material is 4.3 μ m, and the luminosity under wavelength 147nm vacuum ultraviolet rays excites is 103, and after handling 2h under 500 ℃ the temperature, its luminosity is 90 with this fluorescent material.
Adopt the data contrast of the inventive method blue aluminate fluorescent powder that makes and the blue aluminate fluorescent powder that adopts traditional method to make emissive porwer before and after thermal treatment, as shown in table 1.
Table 1 adopts the data contrast of the inventive method fluorescent material that makes and the fluorescent material that adopts traditional method to make luminosity before and after thermal treatment
Table 1 shows, the luminosity of fluorescent material before and after thermal treatment that adopts the inventive method to make all is higher than the luminosity of the fluorescent material that traditional method makes.
Fig. 2 is the emmission spectrum comparison diagram under wavelength excites for the 147nm vacuum ultraviolet rays before and after the fluorescent material thermal treatment that makes of the fluorescent material that makes of embodiment 14 and Comparative Examples 2, wherein, A represents the preceding spectral radiation curves of blue aluminate fluorescent powder thermal treatment that embodiment 14 makes, B represents the preceding spectral radiation curves of blue aluminate fluorescent powder thermal treatment that Comparative Examples 2 makes, C represents the spectral radiation curves after the blue aluminate fluorescent powder thermal treatment that embodiment 14 makes, and D represents the spectral radiation curves after the blue aluminate fluorescent powder thermal treatment that Comparative Examples 24 makes.The fluorescent material that adopts the inventive method to make as can be seen from Figure all is better than the fluorescent material that traditional method makes on luminous intensity and stability.
Claims (7)
1. the preparation method of a blue aluminate fluorescent powder with high brightness and high stability, relating to chemical expression is Ba
0.9MgAl
10O
17: 0.1Eu
2+The preparation of blue aluminate fluorescent powder, it is characterized in that this method is carried out according to the following steps:
Step 1: by the stoichiometric ratio of above-mentioned fluorescent material chemical expression, get aluminum oxide, aluminium nitride, barium salt, magnesium oxide and europium sesquioxide respectively, form starting raw material,
Get fusing assistant,
In the ratio that adds 100ml～150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol,
Above-mentioned starting raw material, fusing assistant and dehydrated alcohol are mixed, and ball milling 10 hours～24 hours obtains raw material powder;
Perhaps, stoichiometric ratio by above-mentioned fluorescent material is got aluminum oxide, aluminium nitride, barium salt, magnesium oxide and europium sesquioxide respectively, form starting raw material, again in the ratio that adds 100ml～150ml dehydrated alcohol in the 7.3 gram starting raw materials, get dehydrated alcohol, with starting raw material and dehydrated alcohol ball milling 10 hours～24 hours, obtain raw material powder;
Step 2: the raw material powder that step 1 is obtained places the environment of bubbling air or reducing atmosphere, temperature rise rate with 5 ℃/min～10 ℃/min, envrionment temperature is risen to 1100 ℃～1700 ℃, be incubated 2 hours～10 hours, then, be cooled to room temperature, this process is carried out once or twice, obtains the powder after the roasting;
Step 3: with the powder after the roasting in the step 2, under condition of stirring, put into dilute hydrochloric acid successively and deionized water washs once at least, oven dry;
Step 4: with ball milling a little less than the powder after step 3 oven dry 1 time～2 times, and use deionized water wash, after the oven dry, sieve, make the blue aluminate fluorescent material of high brightness and high stability.
2. according to the described preparation method of claim 1, it is characterized in that the barium salt in the described step 1 adopts barium sulfate or barium carbonate.
3. according to the described preparation method of claim 1, it is characterized in that, fusing assistant in the described step 1 adopts a kind of in bicarbonate of ammonia, aluminum fluoride, Quilonum Retard or the boric acid, perhaps two kinds combination, when the fusing assistant that adopts was a kind of material, the quality of this fusing assistant was 2%～6% of a starting raw material quality, when the fusing assistant that adopts is the combination of two kinds of materials, the quality of this fusing assistant is 1～10% of a starting raw material quality, and to form between two kinds of materials of this fusing assistant be arbitrary proportion.
4. according to the described preparation method of claim 1, it is characterized in that the mixed gas that the reducing atmosphere in the described step 2 adopts per-cent by volume to be made up of the hydrogen of 90%～95% nitrogen and 5%～10%.
5. according to the described preparation method of claim 1, it is characterized in that the temperature of dilute hydrochloric acid and deionized water is 60 ℃～70 ℃ in the described step 3.
6. according to the described preparation method of claim 1, it is characterized in that the rotating speed that weak ball milling adopts in the described step 4 is 10 commentaries on classics/min～30 commentaries on classics/min, the time is 30 minutes～60 minutes.
7. according to the described preparation method of claim 1, it is characterized in that the order number when sieving in the described step 4 is 1250 orders～2500 orders.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241981A (en) * | 2011-03-04 | 2011-11-16 | 厦门通士达新材料有限公司 | Blue luminescent material for energy saving lamp and preparation method thereof |
| CN102719243A (en) * | 2012-06-01 | 2012-10-10 | 华南农业大学 | Manganese ion-activated red long-afterglow luminescent material and preparation method thereof |
| CN102925146A (en) * | 2012-10-24 | 2013-02-13 | 江苏博睿光电有限公司 | Method for manufacturing nitride fluorescent powder |
| CN104629759A (en) * | 2015-02-12 | 2015-05-20 | 杭州电子科技大学 | Method for enhancing emission intensity of strontium aluminate fluorescent powder |
| CN114940901A (en) * | 2022-07-05 | 2022-08-26 | 兰州大学 | Yellow composite fluorescent pigment and preparation method thereof |
-
2010
- 2010-05-29 CN CN 201010190840 patent/CN101831293B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 《Electrochemical and Solid-State Letters》 20091217 Bitao Liu et al. Photoluminescence Properties and Degradation Mechanisms of BaMgAl10O17:Eu2+ Phosphor under Baking Treatment 第J15－J17页 1－7 第13卷, 第3期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241981A (en) * | 2011-03-04 | 2011-11-16 | 厦门通士达新材料有限公司 | Blue luminescent material for energy saving lamp and preparation method thereof |
| CN102719243A (en) * | 2012-06-01 | 2012-10-10 | 华南农业大学 | Manganese ion-activated red long-afterglow luminescent material and preparation method thereof |
| CN102925146A (en) * | 2012-10-24 | 2013-02-13 | 江苏博睿光电有限公司 | Method for manufacturing nitride fluorescent powder |
| CN102925146B (en) * | 2012-10-24 | 2015-04-29 | 江苏博睿光电有限公司 | Method for manufacturing nitride fluorescent powder |
| CN104629759A (en) * | 2015-02-12 | 2015-05-20 | 杭州电子科技大学 | Method for enhancing emission intensity of strontium aluminate fluorescent powder |
| CN114940901A (en) * | 2022-07-05 | 2022-08-26 | 兰州大学 | Yellow composite fluorescent pigment and preparation method thereof |
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| CN101831293B (en) | 2013-03-06 |
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