CN101665688B - Preparation method of superfine high brightness fluorescent powder - Google Patents
Preparation method of superfine high brightness fluorescent powder Download PDFInfo
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- CN101665688B CN101665688B CN200910035377XA CN200910035377A CN101665688B CN 101665688 B CN101665688 B CN 101665688B CN 200910035377X A CN200910035377X A CN 200910035377XA CN 200910035377 A CN200910035377 A CN 200910035377A CN 101665688 B CN101665688 B CN 101665688B
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Abstract
The invention relates to a preparation method of superfine high brightness fluorescent powder, which comprises the following steps: using prior fine grain diameter long afterglow fluorescent powder for preparing the superfine high brightness long afterglow fluorescent powder, so as to obtain the long afterglow fluorescent powder with the grain diameter smaller than 5 microns but the luminous brightness equivalent to the commercial 15-micron brightness, coating a layer of high melting point oxide Al2O3 on the surface of fine grain diameter long afterglow fluorescent powder grains, high temperature restoring the fluorescent powder coated with the Al2O3 in a reducing atmosphere of 1200-1400 DEG C, and using an isolation function of the Al2O3 for the fluorescent powder in the restoration process to avoid the secondary rigid aggregation of the fluorescent powder grains. The related Al2O3 coating film has the chemical reaction formula of Al<3+>+3OH<->=Al(OH)3, and the reaction is carried out in an anhydrous system.
Description
Technical field
The present invention relates to a kind of preparation method of ultra-fine grain diameter long persistence luminescent powder.The technical field that belongs to the fluorescent material preparation.
Background technology
Long after glow luminous material has another name called noctilucent material, is a kind of of embedded photoluminescent material.It is one type and absorbs the light that sunshine or source of artificial light produced and send visible light, and still can continue luminous material after stopping exciting.Alkaline earth aluminate series luminescent material is the best light-storing and emitting material of present known luminescent properties.Long after glow luminous material with traditional sulfide series is compared, and alkaline earth aluminate series luminescent material has long, radiationless, advantage such as chemical property is stablized after time.
The aluminate long afterglow powder adopts high temperature solid-state method preparation usually, and gained long persistence luminescent powder pellet hardness is very big, must carry out that roller is broken, Hubei Province is broken, airflow milling; Time consumption and energy consumption; Destroy crystallization, the gained powder is compared with former powder agglomates product behind the ball milling, and the luminosity decay is serious.Particle diameter is less than the SrAl2O4:Eu of 5um, and Dy fluorescent material brightness very low (less than 30mcd/m2) is very limited in practical applications such as luminous fabric, luminescent fibre.SrAl2O4:Eu, Dy fluorescent material is through in 1200～1400 ℃ of reducing atmospheres once more behind the high-temperature reply, because the fluorescent powder grain surface obtains repairing, crystalline structure is able to perfect, brightness can obviously improve, but fluorescent material sintering and make hardness become very big once more.Therefore difficulty is very big technically to obtain the long persistence luminescent powder of ultra-fine grain diameter and high brightness.
Chinese patent ZL200610019315.6 discloses a kind of method of using sol-gel method to prepare the superfine aluminate long persistence luminescent powder, and patent ZL200610019316.0 discloses a kind of coprecipitation method of using and combined microwave process for synthesizing to prepare the method for superfine aluminate long persistence luminescent powder.But this fluorescent material need could obtain good luminous property through high-temperature calcination in 1200～1400 ℃ of reducing atmospheres; Can prepare the superfine presoma though use sol-gel method or coprecipitation method; But can sintering take place equally and cause hardness very big in later stage high temperature reduction process, if reduce the long persistence luminescent powder that synthesis temperature then can't obtain high brightness.
Summary of the invention
Technical problem: the present invention proposes a kind of preparation method of superfine high brightness fluorescent powder; Utilize existing fine grain size long persistence luminescent powder to prepare the superfine high brightness long persistence luminescent powder; The long persistence luminescent powder particle diameter that obtains is less than 5 μ m, but luminosity is suitable with commercial 15 μ m brightness.
Technical scheme: the preparation method of superfine high brightness fluorescent powder of the present invention coats the dystectic Al of one deck at fine grain size long persistence luminescent powder particle surface
2O
3Oxide compound, and will coat Al
2O
3After fluorescent material high-temperature reply in 1200～1400 ℃ of reducing atmospheres, utilize Al
2O
3In Recovery Process,, avoid fluorescent powder grain secondary hard aggregation, the Al that relates to the buffer action of fluorescent material
2O
3Coating reactive chemistry formula is Al
3++ 3OH
-=Al (OH)
3, this is reflected in the anhydrous system and carries out, and cladding process comprises following step:
1) long persistence luminescent powder is dispersed in the terepthaloyl moietie, is mixed with the phosphor suspension that concentration is 1～10g/100ml;
2) press Al
2O
3With the weight ratio of fluorescent material be (0.5～10): 100 ratio takes by weighing the Al (NO) of respective amount
39H
2O adds in the phosphor suspension, stirs ultra-sonic dispersion 5～30min simultaneously, and fluorescent material is fully disperseed;
3) phosphor suspension is heated to 80～90 ℃ and temperature controlled this interval, stirs with 50r/m～300r/m speed;
4) ethanol solution of the KOH of compound concentration 0.1～10g/100m or NaOH; This solution is splashed in the phosphor suspension; Rate of addition is 0.5～10ml/min; Regulate phosphor suspension pH meter displayed value to 3～6, drip and finish the continued stirring and be incubated 0.5～8 hour, obtain capsule luminescent powder suspension;
5) with the capsule luminescent powder suspension spinning, wash 1～3 time with ethanol again, fully 200～400 ℃ of 1～3h of calcination again after the oven dry can get Al after the cooling
2O
3The long persistence luminescent powder of coating;
6) with coating steady persistence powder high-temperature reply in 1200～1400 ℃ of reducing atmospheres, can get superfine high brightness degree long persistence luminescent powder after the cooling.
The phosphor suspension temperature maintenance is in 80～90 ℃ of intervals.
Phosphor suspension pH meter displayed value is controlled between 3～6.
Drip and finish continued insulation 0.5～8 hour.
Beneficial effect: advantage of the present invention is: (1) utilizes Al
2O
3The buffer action of film when high-temperature reply improves brightness, keeps granularity not have basically to increase; (2) all coating process carries out in anhydrous system, has avoided the degradation of the long persistence luminescent powder in the coating process.The TEM photo of the superfine high brightness degree long persistence luminescent powder of preparing is seen accompanying drawing.
Description of drawings
Fig. 1 is an experimental considerations synoptic diagram of the present invention.
Embodiment
Coat the dystectic Al of one deck at fine grain size long persistence luminescent powder particle surface
2O
3Oxide compound will coat Al
2O
3After fluorescent material high-temperature reply in 1200～1400 ℃ of reducing atmospheres, utilize Al
2O
3In Recovery Process,, avoid fluorescent powder grain secondary hard aggregation to the buffer action of fluorescent material.Experimental considerations is illustrated in fig. 1 shown below.
Wherein, Al
2O
3The related reaction formula of coating reaction is:
Al
3++3OH
-＝Al(OH)
3
For avoiding the performance loss of fluorescent material in the coating process, total overall reaction is carried out in anhydrous system.
Preparation technology of the present invention comprises following step:
1) long persistence luminescent powder is dispersed in the terepthaloyl moietie, is mixed with the phosphor suspension that concentration is 1～10g/100ml;
2) press Al
2O
3With the weight ratio of fluorescent material be (0.5～10): 100 ratio takes by weighing the Al (NO) of respective amount
39H
2O adds in the phosphor suspension, stirs ultra-sonic dispersion 5～30min simultaneously, and fluorescent material is fully disperseed;
3) phosphor suspension is heated to 80～90 ℃ and with temperature control around here, stirs with 50r/m～300r/m speed;
4) ethanol solution of the KOH of compound concentration 0.1～10g/100m or NaOH; This solution is splashed in the phosphor suspension; Rate of addition is 0.5～10ml/min; Regulate phosphor suspension pH meter displayed value to 3～6, drip and finish the continued stirring and be incubated 0.5～8 hour, obtain capsule luminescent powder suspension;
5) with the capsule luminescent powder suspension spinning, wash 1～3 time with ethanol again, 200～400 ℃ of calcination 1～3h that fully are expert at after the oven dry can get the coating long persistence luminescent powder after the cooling.
6) with coating steady persistence powder high-temperature reply in 1200～1400 ℃ of reducing atmospheres, can get superfine high brightness degree long persistence luminescent powder after the cooling.
Embodiment 1
Taking by weighing medium particle diameter is aluminate long afterglow fluorescent material 20 grams of 4 μ m, and spent glycol is mixed with the phosphor suspension that concentration is 2g/100ml; Take by weighing Al (NO)
39H
2O 1 gram adds in the phosphor suspension, stirs ultra-sonic dispersion 30min simultaneously.Suspension-s is heated to 80 ℃ and keep, stirs simultaneously.The ethanol solution of the KOH of compound concentration 0.1～10g/100m adds this drips of solution in the phosphor suspension, and rate of addition is 2ml/min; The pH meter displayed value of regulating and controlling phosphor suspension is 4; Stop to drip, continue insulation and stir 4h, the suspension-s spinning; Wash 2 times through absolute ethyl alcohol again, use the baking oven thorough drying.With coated fluorescent powder at 300 ℃ of roasting 1h.With the fluorescent material behind the coating at 1300 ℃ of N
2+ H
2Calcining is 3 hours in the reducing atmosphere, can obtain superfine high brightness degree aluminate long afterglow fluorescent material after the cooling.
Embodiment 2
Taking by weighing medium particle diameter is aluminate long afterglow fluorescent material 20 grams of 4 μ m, and spent glycol is mixed with the phosphor suspension that concentration is 2g/100ml; Take by weighing Al (NO)
39H
2O 1 gram adds in the phosphor suspension, stirs ultra-sonic dispersion 30min simultaneously.Suspension-s is heated to 90 ℃ and keep, stirs simultaneously.All the other conditions are with embodiment 1.
Embodiment 3
Taking by weighing medium particle diameter is aluminate long afterglow fluorescent material 20 grams of 4 μ m, and spent glycol is mixed with the phosphor suspension that concentration is 2g/100ml; Take by weighing Al (NO)
39H
2O 1 gram adds in the phosphor suspension, stirs ultra-sonic dispersion 30min simultaneously.Suspension-s is heated to 80 ℃ and keep, stirs simultaneously.The ethanol solution of the KOH of compound concentration 0.1～10g/100m adds this drips of solution in the phosphor suspension, and rate of addition is 2ml/min, and the pH meter displayed value of regulating and controlling phosphor suspension is 5.All the other conditions are with embodiment 1.
Embodiment 4
Taking by weighing medium particle diameter is aluminate long afterglow fluorescent material 20 grams of 4 μ m, and spent glycol is mixed with the phosphor suspension that concentration is 2g/100ml; Take by weighing Al (NO)
39H
2O 1 gram adds in the phosphor suspension, stirs ultra-sonic dispersion 30min simultaneously.Suspension-s is heated to 80 ℃ and keep, stirs simultaneously.The ethanol solution of the KOH of compound concentration 0.1～10g/100m adds this drips of solution in the phosphor suspension, and rate of addition is 2ml/min, and the pH meter displayed value of regulating and controlling phosphor suspension is 6, stops to drip, and continue insulation and stir 8h.All the other conditions are with embodiment 1.
Claims (3)
1. the preparation method of a superfine high brightness fluorescent powder is characterized in that coating the dystectic Al of one deck at fine grain size long persistence luminescent powder particle surface
2O
3Oxide compound, and will coat Al
2O
3After fluorescent material high-temperature reply in 1200～1400 ℃ of reducing atmospheres, utilize Al
2O
3In Recovery Process,, avoid fluorescent powder grain secondary hard aggregation, the Al that relates to the buffer action of fluorescent material
2O
3Coating reactive chemistry formula is Al
3++ 3OH
-=Al (OH)
3, this is reflected in the anhydrous system and carries out, and cladding process comprises following step:
1) is that the aluminate long afterglow fluorescent material of 4 μ m is dispersed in the terepthaloyl moietie with medium particle diameter, is mixed with the phosphor suspension that concentration is 1～10g/100ml;
2) press Al
2O
3With the weight ratio of fluorescent material be (0.5～10): 100 ratio takes by weighing the Al (NO) of respective amount
39H
2O adds in the phosphor suspension, stirs ultra-sonic dispersion 5～30min simultaneously, and fluorescent material is fully disperseed;
3) phosphor suspension is heated to 80～90 ℃ and temperature controlled this interval, stirs with 50r/min～300r/min speed;
4) ethanol solution of the KOH of compound concentration 0.1～10g/100ml or NaOH; This solution is splashed in the phosphor suspension; Rate of addition is 0.5～10ml/min; Regulate phosphor suspension pH meter displayed value to 3～6, drip and finish the continued stirring and be incubated 0.5～8 hour, obtain capsule luminescent powder suspension;
5) with the capsule luminescent powder suspension spinning, wash 1～3 time with ethanol again, fully 200～400 ℃ of 1～3h of calcination again after the oven dry can get Al after the cooling
2O
3The long persistence luminescent powder of coating;
6) with coating steady persistence powder high-temperature reply in 1200～1400 ℃ of reducing atmospheres, can get superfine high brightness degree long persistence luminescent powder after the cooling.
2. the preparation method of a kind of superfine high brightness fluorescent powder according to claim 1 is characterized in that phosphor suspension pH meter displayed value is controlled between 3～6.
3. the preparation method of a kind of superfine high brightness fluorescent powder according to claim 1 is characterized in that dripping end continued insulation 0.5～8 hour.
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| CN102703056B (en) * | 2012-05-09 | 2014-06-25 | 苏州英特华照明有限公司 | Compound enveloped LED (light-emitting diode) phosphor powder grain and enveloping method thereof |
| CN104119885A (en) * | 2013-04-27 | 2014-10-29 | 财团法人纺织产业综合研究所 | Wavelength-migrated composite light-accumulating powder as well as manufacturing method and application of wavelength-migrated composite light-accumulating powder |
| CN105256373A (en) * | 2015-11-09 | 2016-01-20 | 东南大学 | Method for preparing superfine nano powder by introducing airflow |
| CN106190098B (en) * | 2016-06-28 | 2018-06-15 | 浙江晶能荧光材料有限公司 | The preparation method of fluorescent-lamp-use long-life low mercury consumption halogen calcium phosphate fluoressent powder |
| CN110386822B (en) * | 2018-04-19 | 2021-02-26 | 深圳光峰科技股份有限公司 | Complex phase fluorescent ceramic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6398983B1 (en) * | 2001-01-12 | 2002-06-04 | Harvatek Corporation | Fluorescent material for packaging optical devices |
| CN1861738A (en) * | 2006-06-09 | 2006-11-15 | 江西财经大学 | Surface alumina oxide compact film coating process of long afterglow luminescent powder of alkaline earth aluminate |
| CN1900216A (en) * | 2005-07-22 | 2007-01-24 | 北京大学 | Process for preparing rare-earth excited strontium aluminate long afterglow fluorescent powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6398983B1 (en) * | 2001-01-12 | 2002-06-04 | Harvatek Corporation | Fluorescent material for packaging optical devices |
| CN1900216A (en) * | 2005-07-22 | 2007-01-24 | 北京大学 | Process for preparing rare-earth excited strontium aluminate long afterglow fluorescent powder |
| CN1861738A (en) * | 2006-06-09 | 2006-11-15 | 江西财经大学 | Surface alumina oxide compact film coating process of long afterglow luminescent powder of alkaline earth aluminate |
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