CN1294170A - Combustion process for preparing long-afterglow phosphorescent powder - Google Patents

Combustion process for preparing long-afterglow phosphorescent powder Download PDF

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CN1294170A
CN1294170A CN 99117330 CN99117330A CN1294170A CN 1294170 A CN1294170 A CN 1294170A CN 99117330 CN99117330 CN 99117330 CN 99117330 A CN99117330 A CN 99117330A CN 1294170 A CN1294170 A CN 1294170A
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long
combustion process
phosphorescent powder
afterglow
afterglow phosphorescent
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CN1102170C (en
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陈仲林
张玉奇
万体智
严德忠
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CHONGQING ARCHITECTURE UNIV
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CHONGQING ARCHITECTURE UNIV
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Abstract

A combustion process for preparing long-afterglow phosphorescent powder includes proportionally preparing aqueous solution of nitrate from raw materials, adding organic fuel, flux and combustion promoter, loading in quartz utensil, heating to evaporating the solution for higher concentration, burning in muffle furnace for several min and grinding to obtain nm powder.

Description

Combustion process for preparing long-afterglow phosphorescent powder
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 the journal NO.1 of Fudan University in 1997 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 long-afterglow material adopts the high temperature solid-state method preparation more, its synthetic crystal grain degree is bigger, and the demand of society 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 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 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, promptly earlier be heated rapidly to 200 ℃～400 ℃ with hot-plate, its solution is evaporated to thicken, entering into furnace temperature more immediately is 500 ℃～900 ℃ retort furnace or special roasting kiln, and remove air in the replacement(metathesis)reaction stove with rare gas element or nitrogen, 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, again through in the darkroom, screening after the illumination, acceptable material is worn into powder, its crystal particle diameter can reach nano level, promptly gets long-afterglow phosphorescent powder.
Also can in proportion raw material be made purified nitrate aqueous solution, and add an amount of organic-fuel and fusing assistant and combustion adjuvant, place in the container, directly move on to furnace temperature again and be in 500 ℃～900 ℃ the retort furnace, 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, promptly get long-afterglow phosphorescent powder.
One or more that phosphor material of the present invention is an alkaline earth salt are 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 it is that the prescription (weight percent) of the long-afterglow material of matrix is as follows with the alkaline earth salt:
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％。
In the burning preparation process, the add-on of fusing assistant is: B 2O 3(0～16%) or H 3BO 3(0～20%); The reductive agent that adds is glycine or oxalic acid or urea or hydrazine class organic-fuel; Adding the nitrate of oxygenant and the stoichiometric mol ratio of the organic-fuel that adds reductive agent is 1: 1～1: 10; To the add-on ammonium nitrate of its combustion adjuvant be 0～30% or ammonium chlorate be 0～40% or nitric acid be 0～60%.
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, the container that fills this mixture is positioned over the retort furnace with certain furnace temperature or places 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 of the phosphorescent substance that is made by combustion method 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, can prepare the long-afterglow material of littler crystal grain, has 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 phosphor powder crystal grain diameter 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 is applicable to guidance lighting and decorative illuminations such as making 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 the room temperature redilution 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 waiting to dissolve cooling, is diluted to 25ml.
4. take by weighing Dy 2O 3(3N) 2.331g, 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 diluted to 25ml.
5. take by weighing analytical pure H 3BO 31.546g, after being dissolved in water, be diluted to 50ml.
Above-mentioned solution is pressed volume ratio accurately:
Sr (NO 3) 2: Al (NO 3) 3: Eu (NO 3) 3: Dy (NO 3) 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 cabinet-type electric furnace of protection, the spontaneous combustion reaction takes place promptly after 1 minute～5 minutes, burning continues to finish after tens of seconds, promptly gets the spumescence long after glow luminous material that loosens after the taking-up cooling, is the long-afterglow phosphorescent powder product behind the porphyrize.

Claims (10)

1. combustion process for preparing long-afterglow phosphorescent powder, adopt the low-temperature burning composite phosphor, its prescription is alkaline earth salt: europium, add more than one rare earth element, in proportion raw material is made purified nitrate aqueous solution, and add an amount of 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, with the air in rare gas element or the nitrogen replacement Reaktionsofen, makes the stove district be in anoxic condition in stove, 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, and particle diameter can reach nano level, promptly gets long-afterglow phosphorescent powder.
2. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, in proportion raw material is made purified nitrate aqueous solution, and add an amount of fuel and fusing assistant and combustion adjuvant, place in the container, directly move on to furnace temperature again and be in 500 ℃～900 ℃ the retort furnace, 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, promptly get long-afterglow phosphorescent powder.
3. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, one or more that its phosphor material is an alkaline earth salt are matrix, divalent europium is an activator, and one or more among rare earth element Pr, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu are sensitizing agent; Its alkaline earth salt 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) 2 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. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, its fusing assistant B 2O 3Add-on is 0～16%.
5. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, its fusing assistant H 3BO 3Add-on is 0～20%.
6. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, its reductive agent are glycine.
7. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, its reductive agent are urea.
8. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, it is 1: 1～1: 10 as the nitrate of oxygenant with as the organic-fuel stoichiometry mol ratio of reductive agent.
9. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, the add-on of its combustion adjuvant ammonium nitrate are 0～30%.
10. combustion process for preparing long-afterglow phosphorescent powder as claimed in claim 1, the add-on of its combustion adjuvant nitric acid are 0～60%.
CN 99117330 1999-10-29 1999-10-29 Combustion process for preparing long-afterglow phosphorescent powder Expired - Fee Related CN1102170C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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
CN102367384A (en) * 2011-10-29 2012-03-07 南昌大学 Preparation method of flaky aluminate green phosphor
CN101386784B (en) * 2008-09-05 2013-06-26 陈哲 Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion

Cited By (5)

* Cited by examiner, † Cited by third party
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
CN102367384A (en) * 2011-10-29 2012-03-07 南昌大学 Preparation method of flaky aluminate green phosphor

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