CN1102170C - Combustion process for preparing long-afterglow phosphorescent powder - Google Patents
Combustion process for preparing long-afterglow phosphorescent powder Download PDFInfo
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- CN1102170C CN1102170C CN 99117330 CN99117330A CN1102170C CN 1102170 C CN1102170 C CN 1102170C CN 99117330 CN99117330 CN 99117330 CN 99117330 A CN99117330 A CN 99117330A CN 1102170 C CN1102170 C CN 1102170C
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- phosphorescent powder
- combustion process
- afterglow
- afterglow phosphorescent
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Abstract
The present invention relates to long afterglow phosphor powder whose application range belongs to the field of lighting engineering. The present invention aims at solving the technical problem that the long afterglow phosphor powder is prepared by a low temperature burning method. The present invention has the main technical characteristics that raw materials are firstly prepared into a purified nitrate water solution proportionally, and proper quantities of organic fuels, fluxing agents and combustion adjuvant are added; the raw materials and the auxiliary materials are put in a silica ware; a two-step heating method is used, and the two-step heating method is characterized in that firstly, the solution is heated for evaporation so as to be thickened, then, the solution is moved into a muffle furnace for combustion synthesis, which can obtain long afterglow phosphorescent materials through several minutes only, and then, qualified materials are ground into powder whose crystal grain size can reach a nanometer grade. The long afterglow phosphor powder is suitable for printing, and can also be used for the indication and the illumination of light emission decoration, handicrafts, various liquor light marks, etc.
Description
The range of application of long-afterglow phosphorescent powder belongs to the illuminating engineering field.
The present domestic and international research direction in this field mostly is the preparation lamp phosphor, prepares lamp phosphor as 1997 multiple day college journal No.1 with combustion method; And for example application for a patent for invention number 91107337 usefulness high temperature solid-state methods prepare long-afterglow material, i.e. luminescent coating, and its delay time adopts high temperature solid-state method for can reach tens to tens hours for the preparation of long persistence phosphor more, and temperature is 1200 ℃～1600 ℃; The and for example preparation of chlorate MClO 3 fluorescent substance, Japan adopts high temperature solid-state method, and temperature is 1600 ℃～2000 ℃, the preparation lamp phosphor.
Purpose of the present invention, in view of existing twilight sunset material adopts the high temperature solid-state method preparation more, its synthetic crystal grain degree is bigger, and the social demand amount is big, the special combustion process for preparing long-afterglow phosphorescent powder of developing, adopt the SILVER REAGENT raw material, prepare long-afterglow phosphorescent powder with low-temperature combustion method, this method preparation is quick, process controllability is good, range of application is more extensive.
The present invention is a combustion process for preparing long-afterglow phosphorescent powder, adopt the combustion process for preparing composite phosphor, its prescription is aluminium salt, alkaline earth salt, europium, other adds more than one other rare earth elements, in proportion raw material is made purified nitrate aqueous solution, and add an amount of organic-fuel urea or glycine (as reductive agent) and fusing assistant and combustion adjuvant, place in the quartz apparatus or porcelain crucible (non-metallic vessel), the volumetric ratio of its combustion substance and container is 0.02g/ml～0.2g/ml, adopt the heating of two steps, earlier being heated rapidly to 200 ℃～400 ℃ with hot-plate thickens solution evaporation, entering into furnace temperature more immediately is 500 ℃～900 ℃ retort furnace or special roasting kiln, in stove with the air in rare gas element or the nitrogen replacement Reaktionsofen, make the stove district be in anoxic condition, material is lighted, its heating rate is 40 ℃/min～300 ℃/min, through burning is the synthesizing long-persistence phosphor material, and with its cooling, through in the darkroom, screening after the illumination, acceptable material is worn into powder, particle diameter can reach nano level, promptly gets long-afterglow phosphorescent powder.
Also can be in proportion raw material aluminium salt, alkaline earth salt, europium sesquioxide, other rare earth oxide of adding more than one be made into purified nitrate aqueous solution, and add an amount of organic-fuel urea or glycine (as reductive agent) and fusing assistant and combustion adjuvant, place in the quartz apparatus or porcelain crucible, directly move on to furnace temperature then and be in 500 ℃～900 ℃ the retort furnace or in the special roasting kiln (a step heating flame), promptly generate long-decay phosphor material through combustion reactions, promptly get the long-afterglow phosphorescent powder product through crushing and classification again.
Phosphor material of the present invention is that alkali earth metal aluminate is a matrix, divalent europium is an activator, among rare earth element Pr, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu one or more are for being total to sensitizing agent, and its alkali earth metal aluminate is that the prescription (weight percent) of the long-afterglow material of matrix is as follows:
Al(NO
3)
3 35～85％ Ca(NO
3)
2 0～40％
Mg(NO
3)
2 0～30％ Ba(NO
3)
2 0～60％
Zn(NO
3)
2 0～45％ Sr(NO
3)
2 0～50％
Eu(NO
3)
3 0.01～10％ Pr(NO
3)
4 0～10％
Pr(NO
3)
3 0～10％ Gd(NO
3)
3 0～10％
Tb(NO
3)
3 0～5％ Tb(NO
3)
4 0～5％
Dy(NO
3)
3 0.01～10％ Ho(NO
3)
3 0～10％
Er(NO
3)
3 0～10％ Tm(NO
3)
3 0～10％
Yb(NO
3)
3 0～10％ Lu(NO
3)
3 0～10％
In the burning preparation process, the add-on of fusing assistant is: B
2O
3＜16%, H
3BO
3＜20% (being the composition of raw materials weight percent); The reductive agent that adds is urea or glycine (being organic-fuel); Adding is 1: 1～1: 10 as the nitrate of oxygenant with as the urea of reductive agent (organic-fuel) or the stoichiometry mol ratio of glycine; Add-on to its combustion adjuvant ammonium nitrate is＜30%, and the add-on of nitric acid is＜60% (being the composition of raw materials weight percent).
The present invention be a kind of not only fast but also prepare the low temperature combustion synthesis method of long-afterglow phosphorescent powder easily, it is raw material that this law adopts nitrate and organic-fuel mixture, be positioned over the container that fills this mixture in the retort furnace with certain furnace temperature or in the special roasting kiln, with certain heating rate heating, after specific temperature down-firing burning, can obtain the loose long-afterglow material of spumescence, whole process only needs several minutes, and the crystal grain diameter by the phosphorescent substance of combustion method preparation can reach nano level, crystal shape behind pulverize is damaged hardly, and the difference of the luminosity of the luminosity of powder material and spumescence product is not remarkable.Its outstanding advantage of the long-afterglow material of low-temperature combustion method preparation is that ignition temperature is low, the technological process controllability is good, compare with high temperature solid-state method, can prepare the long-afterglow material of littler crystal grain, have purposes more widely, and will have remarkable economic efficiency and social benefit.
Advantage that the present invention has and effect:
1. low temperature rapid combustion is synthetic, saves the energy;
2. the technological process controllability is good;
3. the crystal grain diameter of phosphor powder can reach nano level, and applicable scope is wide;
Time of persistence long, can reach more than 33 hours;
5. compare with the high temperature solid state reaction synthesis method, this law has advantages such as reaction times phosphor material short, that make is loose, hardness is little, crystal particle diameter is little;
6. the long-afterglow phosphorescent powder that makes of the present invention can be used for printing, also can do guidance lighting and decorative illuminations such as luminous ornament, artwork and various noctilucence marks.
Embodiment:
1. take by weighing analytical pure SrCO
311.380g the about 20ml of adding distil water adds analytical pure concentrated nitric acid (65%) 21.4g more while stirring, after the heating for dissolving, is chilled to room temperature and is diluted to 50ml.
2. take by weighing analytical pure Al (NO
3)
39H
2O 37.513g after the adding distil water dissolving, is diluted to 50ml.
3. take by weighing Eu
2O
3(4N) 1.100g, the about 4ml of adding distil water adds analytical pure concentrated nitric acid (65%) 6.9g while stirring, after the dissolving cooling to be heated, is chilled to room temperature and is diluted to 25ml.
4. take by weighing Dy
2O
3(3N) 2.3311g, the about 4ml of adding distil water adds analytical pure concentrated nitric acid (65%) 13.9g while stirring, after the dissolving cooling to be heated, is chilled to room temperature and is diluted to 25ml.
5. take by weighing analytical pure H
3BO
31.546g, after the adding distil water dissolving, be diluted to 50ml.With above-mentioned solution accurately by volume:
Sr (NO
3)
2: Al (NO
3)
3: Eu
2O
3: Dy
2O
3: H
3BO
3=3: 5: 0.5: 0.25: 2.9 taking-ups place a quartz apparatus, and mixing is pressed 3ml Sr (NO again
3)
2Solution adds urea amount 4.8g, directly quickly heats up to 200 ℃～400 ℃ then, and quartz apparatus to be put into furnace temperature be 500 ℃～900 ℃ again and be filled with N
2In the chamber type electric resistance furnace of protection, the spontaneous combustion reaction took place promptly after 1～5 minute, burning continues to finish after tens of seconds, promptly gets the spumescence long after glow luminous material that loosens after the taking-up cooling, promptly gets the long-afterglow phosphorescent powder product behind the porphyrize.
Claims (10)
1. the combustion process for preparing long-afterglow phosphorescent powder of an aluminate substrate, adopt the low-temperature burning composite phosphor, its prescription is aluminium salt, alkaline earth salt, europium, add more than one rare earth element, in proportion raw material is made purified nitrate aqueous solution, and adding amount of urea or glycine (organic-fuel) and fusing assistant and combustion adjuvant, place in the quartz apparatus or porcelain crucible, the volumetric ratio of its combustion substance and container is 0.02g/ml～0.2g/ml, adopt the heating of two steps, earlier being heated rapidly to 200 ℃～400 ℃ with hot-plate thickens solution evaporation, entering into furnace temperature again is 500 ℃～900 ℃ retort furnace or special roasting kiln, in stove with the air in rare gas element or the nitrogen replacement Reaktionsofen, make the stove district be in anoxic condition, material is lighted, its heating rate is 40 ℃/min～300 ℃/min, through burning synthesizing long-persistence phosphor material, and with its cooling, through in the darkroom, screening after the illumination, acceptable material is worn into powder, particle diameter can reach nano level, promptly gets long-afterglow phosphorescent powder.
2. the combustion process for preparing long-afterglow phosphorescent powder of an aluminate substrate adopts the low-temperature burning composite phosphor, its prescription for aluminium salt, alkaline earth salt, europium sesquioxide, add more than one other rare earth oxide.In proportion raw material is made into nitrate aqueous solution, and adding amount of urea or glycine (organic-fuel) and fusing assistant and combustion adjuvant, place in the quartz apparatus or porcelain crucible, directly move on to furnace temperature then and be in 500 ℃～900 ℃ the retort furnace or in the special roasting kiln (a step heating flame), promptly generate long-decay phosphor material through combustion reactions, promptly get the long-afterglow phosphorescent powder product through crushing and classification again.
3. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, its phosphor material is that alkali earth metal aluminate is a matrix, divalent europium is an activator, among rare earth element Pr, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu one or more are sensitizing agent, and its alkali earth metal aluminate is that the prescription (weight percent) of the long-afterglow material of matrix is as follows:
Al(NO
3)
3 35～85％ Ca(NO
3)
2 0～40％
Mg(NO
3)
2 0～30％ Ba(NO
3)
2 0～60％
Zn(NO
3)
2 0～45％ Sr(NO
3)
2 0～50％
Eu(NO
3)
3 0.01～10％ Pr(NO
3)
4 0～10％
Pr(NO
3)
3 0～10％ Gd(NO
3)
3 0～10％
Tb(NO
3)
3 0～5％ Tb(NO
3)
4 0～5％
Dy(NO
3)
3 0～10％ Ho(NO
3)
3 0～10％
Er(NO
3)
3 0～10％ Tm(NO
3)
3 0～10％
Yb(NO
3)
3 0～10％ Lu(NO
3)
3 0～10％
4. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, its fusing assistant B
2O
3Add-on be＜16% (composition of raw materials weight percent).
5. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, its fusing assistant H
3BO
3Add-on be＜20% (composition of raw materials weight percent).
6. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, its organic-fuel is a glycine.
7. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, its organic-fuel is a urea.
8. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, it is 1: 1～1: 10 as the nitrate of oxygenant with as the urea of reductive agent (organic-fuel) or the stoichiometry mol ratio of glycine.
9. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, the add-on of its combustion adjuvant ammonium nitrate is＜30% (composition of raw materials weight percent).
10. as claim 1,2 described combustion process for preparing long-afterglow phosphorescent powder, the add-on of its combustion adjuvant nitric acid is＜60% (composition of raw materials weight percent).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99117330 CN1102170C (en) | 1999-10-29 | 1999-10-29 | Combustion process for preparing long-afterglow phosphorescent powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99117330 CN1102170C (en) | 1999-10-29 | 1999-10-29 | Combustion process for preparing long-afterglow phosphorescent powder |
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|---|---|
| CN1294170A CN1294170A (en) | 2001-05-09 |
| CN1102170C true CN1102170C (en) | 2003-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99117330 Expired - Fee Related CN1102170C (en) | 1999-10-29 | 1999-10-29 | Combustion process for preparing long-afterglow phosphorescent powder |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314776C (en) * | 2004-01-15 | 2007-05-09 | 山东大学 | Method for preparing long aftergrow nano luminous material at low temperature |
| CN1315984C (en) * | 2005-08-02 | 2007-05-16 | 中国计量学院 | Self-ignite preparation method of spherical nanometer Yttrium europium silicate fluorescent powder |
| CN1876757B (en) * | 2006-07-20 | 2010-12-08 | 长春理工大学 | Low temperature combustion synthesis method for converting luminescent material of sulfide |
| CN101386784B (en) * | 2008-09-05 | 2013-06-26 | 陈哲 | Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion |
| CN102367384B (en) * | 2011-10-29 | 2013-06-05 | 南昌大学 | Preparation method of flaky aluminate green phosphor |
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1999
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