CN1940012A - Long-persistence powdery materials by microwave burning foaming method without ball milling process - Google Patents
Long-persistence powdery materials by microwave burning foaming method without ball milling process Download PDFInfo
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Abstract
A non-ball milling ling afterglow powdery material by microwave burning-foaming method is prepared by adding disperser, foaming agent, burning agent and mineralizer into system, and burning-foaming reacting in household microwave oven directly to obtain the final product. It's stable and direct. It can be used for luminescent coating, luminescent thin-film, luminescent ink, luminescent ceramics, luminescent plastic, luminescent fiber, building ornaments, traffic sign and emergent indicator.
Description
Technical field
The invention belongs to the powder luminous material preparing technical field, be specifically related to rare-earth ion activated persistance without ball milling powder body material.
Technical background
As the long afterglow powder luminescent material of one of features luminescent material, because its storage-light characteristics of luminescence is utilized sunlight or light storage light daytime, night is luminous, and these characteristics make its range of application can contain many aspects of industrial and agricultural production and people's life.Long-afterglow material can further make luminous paint, light-emitting film, luminous printing ink, luminescent ceramic, luminescent plastics, luminescent fibre and luminescent paper etc., is used widely in architectural decoration, traffic sign, military machine, fields such as emergent indication, workmanship or daily necessities.
According to the retrieval, the method for making of at present domestic and international long-afterglow material mainly comprises following method:
High temperature solid phase synthesis is as Chinese patent CN1344777 etc.; Sol-gel method is as Chinese patent CN1197831A; Microwave process for synthesizing is as Chinese patent CN1396234; Combustion method, as Chinese patent CN1294170A or the like, most methods are high temperature solid phase synthesis.
Summary of the invention
At present, the long afterglow powder material at home and abroad has broad prospects on the market as a kind of emerging high-tech product, be in great demand, and in rising trend year by year.Because developing rapidly and actual needs of science and technology, press for a kind of under the prerequisite that does not influence luminescent properties the diameter of particle of material as much as possible little, and size distribution wants uniform method to prepare the persistance without ball milling powder body material.The object of the present invention is to provide a kind of without ball milling, particle diameter can reach micron order, with low cost, preparation technology is simple and the preparation method of the long-afterglow material of favorable reproducibility.Technical problem underlying to be solved by this invention and the technical scheme that solves its technical problem comprise:
1, preparation process comprises:
1) a kind of organic polymer dispersion agent is joined Sr, Al, Eu makes modified solution, induction stirring 10min in the nitrate mixed solution of Dy;
2) whipping agent with a kind of organic macromolecule joins in the above-mentioned modified solution, continues to stir 10min;
3) add incendiary material then, stir 10min, make it be dissolved in the system fully;
4) add the mineralizer powder, it be dispersed in the system, then in 85 ℃ of evaporation at constant temperatures until thickness slightly;
5) transfer in the crucible according to certain liquid volume and crucible volume ratio then, directly place the household microwave oven internal heating after adding a cover, burning is suddenly burnt-foamable reaction after several minutes, keeps after about about one minute and extinguishes gradually;
6) move rapidly as in the retort furnace that is heated to certain temperature in advance after the taking-up, take out after placing for some time, promptly obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
2, above-mentioned steps 1) in the organic polymer dispersion agent be polyoxyethylene glycol (PEG), effective mol ratio of described dispersion agent and metal ion is 0.5: 1～1: 1.
3, above-mentioned steps 2) in the organic macromolecule whipping agent can be in citric acid or the glucose one or both, effective mol ratio of described whipping agent and metal ion is 0.05: 1～0.1: 1.
4, above-mentioned steps 3) in incendiary material can be urea, glycine and carbohydrazide, effective mol ratio of described incendiary material and metal ion is 10: 1～20: 1.
5, above-mentioned steps 4) in the mineralizer powder can be boric acid or B
2O
3In the powder one or both, effective mol ratio of described mineralizer and metal ion is 0.025: 1～0.1: 1.
6, above-mentioned steps 5) in liquid volume and crucible volume ratio be 1: 10～1: 4.
7, above-mentioned steps 5) in household microwave oven power be 600-800W, heat-up time 10-20min.
8, above-mentioned steps 6) in muffle furnace be 600-800 ℃, storage period 10-20min.
Persistance without ball milling powder body material technology of preparing of the present invention has following characteristics:
1) utilize nitrate and organic-fuel etc. as raw materials for production, with low cost; 2) in system, add organic polymer dispersion agent and macromole whipping agent, utilize organic network dispersion effect of macromolecular compound and organic macromolecule to be subjected to the synergy that high temperature after foaming effect combines, intercept the reunion and the combination of ultrafine particulate; 3) comprehensively adjust dispersion agent and whipping agent addition and ratio, make products of combustion fluffy, even, and become powder after not needing ball milling directly to crush, particle diameter is tiny, can reach micron order; 4) put into microwave oven after the crucible that mixing liquid directly will be housed is added a cover and burn-foamable reaction, obtain spumescence long afterglow powder material at last, whole process only needs tens of minutes, has shortened the time greatly; 5) gas ratio that discharges in the combustion processes in the environment is less; 6) the simple and favorable reproducibility of preparation technology is saved the energy.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1:
With 0.211g europium sesquioxide and 0.446g dysprosium oxide distilled water furnishing pulpous state, the concentrated nitric acid dissolving that splashes into 14mol/L in the time of heating is until being colourless transparent solution.4.232g strontium nitrate and 15.006g aluminum nitrate are joined in the 25mL distilled water, and induction stirring is dissolved fully until nitrate.The mixed solution continuation stirring that rare-earth ion solution is added strontium, aluminium salt obtains mixing solutions, adds 4.00g (about 3.6mL) polyoxyethylene glycol (PEG200), and adding obtained flaxen mixing solutions with the 0.420g citric acid after constant temperature stirred 10min.Adding 24.024g urea behind the 10min continues to stir, constant temperature adds boric acid powder 0.062g after stirring 10min, continue to stir 10min, move into then in 85 ℃ of thermostat water baths and evaporate, present faint yellow thick until colloidal sol, taking-up 10mL packs in the big corundum crucible of 100mL, directly put into 800W household microwave oven heating 10min after adding a cover, suddenly burning after several minutes, burn-foamable reaction, keep after about about one minute and extinguish gradually, move rapidly after the taking-up, take out after placing 10min as being heated in advance in 600 ℃ the retort furnace, obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
Embodiment 2:
With 0.211g europium sesquioxide and 0.446g dysprosium oxide distilled water furnishing pulpous state, the concentrated nitric acid dissolving that splashes into 14mol/L in the time of heating is until being colourless transparent solution.4.232g strontium nitrate and 15.006g aluminum nitrate are joined in the 25mL distilled water, and induction stirring is dissolved fully until nitrate.The mixed solution continuation stirring that rare-earth ion solution is added strontium, aluminium salt obtains mixing solutions, adds 8.00g (about 7.2mL) polyoxyethylene glycol (PEG200), and adding obtained flaxen mixing solutions with 0.396g glucose after constant temperature stirred 10min.Adding the 30.028g glycine behind the 10min continues to stir, constant temperature adds boric acid powder 0.124g after stirring 10min, continue to stir 10min, move into then in 85 ℃ of thermostat water baths and evaporate, present faint yellow thick until colloidal sol, taking-up 20mL packs in the big corundum crucible of 100mL, directly put into 600W household microwave oven heating 20min after adding a cover, suddenly burning after several minutes, burn-foamable reaction, keep after about about one minute and extinguish gradually, move rapidly after the taking-up, take out after placing 15min as being heated in advance in 750 ℃ the retort furnace, obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
Embodiment 3:
With 0.211g europium sesquioxide and 0.446g dysprosium oxide distilled water furnishing pulpous state, the concentrated nitric acid dissolving that splashes into 14mol/L in the time of heating is until being colourless transparent solution.4.232g strontium nitrate and 15.006g aluminum nitrate are joined in the 25mL distilled water, and induction stirring is dissolved fully until nitrate.The mixed solution continuation stirring that rare-earth ion solution is added strontium, aluminium salt obtains mixing solutions, adds 6.00g (about 5.4mL) polyoxyethylene glycol (PEG200), and adding obtained flaxen mixing solutions with the 0.841g citric acid after constant temperature stirred 10min.Adding the 72.072g carbohydrazide behind the 10min continues to stir, constant temperature adds boron oxide powder 0.0696g after stirring 10min, continue to stir 10min, move into then in 85 ℃ of thermostat water baths and evaporate, present faint yellow thick until colloidal sol, taking-up 25mL packs in the big corundum crucible of 100mL, directly put into 700W household microwave oven heating 15min after adding a cover, suddenly burning after several minutes, burn-foamable reaction, keep after about about one minute and extinguish gradually, move rapidly after the taking-up, take out after placing 20min as being heated in advance in 700 ℃ the retort furnace, obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
Embodiment 4:
With 0.211g europium sesquioxide and 0.446g dysprosium oxide distilled water furnishing pulpous state, the concentrated nitric acid dissolving that splashes into 14mol/L in the time of heating is until being colourless transparent solution.4.232g strontium nitrate and 15.006g aluminum nitrate are joined in the 25mL distilled water, and induction stirring is dissolved fully until nitrate.The mixed solution continuation stirring that rare-earth ion solution is added strontium, aluminium salt obtains mixing solutions, adds 4.00g (about 3.6mL) polyoxyethylene glycol (PEG200), and adding obtained flaxen mixing solutions with 0.793g glucose after constant temperature stirred 10min.Adding 48.048g urea behind the 10min continues to stir, constant temperature adds boric acid powder 0.247g after stirring 10min, continue to stir 10min, move into then in 85 ℃ of thermostat water baths and evaporate, present faint yellow thick until colloidal sol, taking-up 15mL packs in the big corundum crucible of 100mL, directly put into 800W household microwave oven heating 10min after adding a cover, suddenly burning after several minutes, burn-foamable reaction, keep after about about one minute and extinguish gradually, move rapidly after the taking-up, take out after placing 10min as being heated in advance in 650 ℃ the retort furnace, obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
Embodiment 5:
With 0.211g europium sesquioxide and 0.446g dysprosium oxide distilled water furnishing pulpous state, the concentrated nitric acid dissolving that splashes into 14mol/L in the time of heating is until being colourless transparent solution.4.232g strontium nitrate and 15.006g aluminum nitrate are joined in the 25mL distilled water, and induction stirring is dissolved fully until nitrate.The mixed solution continuation stirring that rare-earth ion solution is added strontium, aluminium salt obtains mixing solutions, adds 6.00g (about 5.4mL) polyoxyethylene glycol (PEG200), and adding obtained flaxen mixing solutions with the 0.630g citric acid after constant temperature stirred 10min.Adding the 36.036g carbohydrazide behind the 10min continues to stir, constant temperature adds boron oxide powder 0.278g after stirring 10min, continue to stir 10min, move into then in 85 ℃ of thermostat water baths and evaporate, present faint yellow thick until colloidal sol, taking-up 15mL packs in the big corundum crucible of 100mL, directly put into 700W household microwave oven heating 15min after adding a cover, suddenly burning after several minutes, burn-foamable reaction, keep after about about one minute and extinguish gradually, move rapidly after the taking-up, take out after placing 10min as being heated in advance in 800 ℃ the retort furnace, obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
Embodiment 6:
With 0.211g europium sesquioxide and 0.446g dysprosium oxide distilled water furnishing pulpous state, the concentrated nitric acid dissolving that splashes into 14mol/L in the time of heating is until being colourless transparent solution.4.232g strontium nitrate and 15.006g aluminum nitrate are joined in the 25mL distilled water, and induction stirring is dissolved fully until nitrate.The mixed solution continuation stirring that rare-earth ion solution is added strontium, aluminium salt obtains mixing solutions, adds 8.00g (about 7.2mL) polyoxyethylene glycol (PEG200), and adding obtained flaxen mixing solutions with 0.595g glucose after constant temperature stirred 10min.Adding the 60.056g glycine behind the 10min continues to stir, constant temperature adds boron oxide powder 0.139g after stirring 10min, continue to stir 10min, move into then in 85 ℃ of thermostat water baths and evaporate, present faint yellow thick until colloidal sol, taking-up 12mL packs in the big corundum crucible of 100mL, directly put into 600W household microwave oven heating 20min after adding a cover, suddenly burning after several minutes, burn-foamable reaction, keep after about about one minute and extinguish gradually, move rapidly after the taking-up, take out after placing 15min as being heated in advance in 700 ℃ the retort furnace, obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
Claims (8)
1. microwave burning-foaming process for preparing powder material in steady persistance without ball milling technology is characterized in that preparation process comprises: 1) a kind of organic polymer dispersion agent is joined Sr, and Al, Eu makes modified solution, induction stirring 10min in the nitrate mixed solution of Dy; 2) whipping agent with a kind of organic macromolecule joins in the above-mentioned modified solution, continues to stir 10min; 3) add incendiary material then, stir 10min, make it be dissolved in the system fully; 4) add the mineralizer powder, it be dispersed in the system, then in 85 ℃ of evaporation at constant temperatures until thickness slightly; 5) transfer in the crucible according to certain liquid volume and crucible volume ratio then, directly place the household microwave oven internal heating after adding a cover, burning is suddenly burnt-foamable reaction after several minutes, and flame is kept after about about one minute and extinguished gradually; 6) taking out the rapid immigration in back is heated in the retort furnace of certain temperature in advance, take out after placing for some time, promptly obtain the foamed persistance without ball milling material of near-white, volumetric expansion several times, quality is loose porous, is subjected to daylight or ultraviolet excitation and has yellow-green colour twilight sunset.
2. by the described method of claim 1, it is characterized in that the organic polymer dispersion agent in the step 1) is polyoxyethylene glycol (PEG), effective mol ratio of described dispersion agent and metal ion is 0.5: 1～1: 1.
3. by the described method of claim 1, it is characterized in that step 2) in the organic macromolecule whipping agent can be in citric acid or the glucose one or both, effective mol ratio of described whipping agent and metal ion is 0.05: 1～0.1: 1.
4. by the described method of claim 1, it is characterized in that the incendiary material in the step 3) can be urea, glycine and carbohydrazide, effective mol ratio of described incendiary material and metal ion is 10: 1～20: 1.
5. by the described method of claim 1, it is characterized in that the mineralizer powder in the step 4) can be boric acid or B
2O
3In the powder one or both, effective mol ratio of described mineralizer and metal ion is 0.025: 1～0.1: 1.
6. by the described method of claim 1, it is characterized in that liquid volume and the crucible volume ratio in the step 5) is 1: 10～1: 4.
7. by the described method of claim 1, it is characterized in that the household microwave oven power in the step 5) is 600-800W, heat-up time 10-20min.
8. by the described method of claim 1, it is characterized in that the muffle furnace in the step 6) is 600-800 ℃, storage period 10-20min.
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| CNB2005101054207A CN100494311C (en) | 2005-09-28 | 2005-09-28 | microwave burning foaming method for preparing long-afterglow powdery materials without ball milling process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456570B (en) * | 2008-12-18 | 2010-12-15 | 上海交通大学 | Method for preparing cerium doped yttrium aluminum garnet |
| CN101386784B (en) * | 2008-09-05 | 2013-06-26 | 陈哲 | Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion |
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2005
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386784B (en) * | 2008-09-05 | 2013-06-26 | 陈哲 | Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion |
| CN101456570B (en) * | 2008-12-18 | 2010-12-15 | 上海交通大学 | Method for preparing cerium doped yttrium aluminum garnet |
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