CN1194066C - Quasi-thin empholite crystal-inoculating rare earth light-emitting material preparing process - Google Patents
Quasi-thin empholite crystal-inoculating rare earth light-emitting material preparing process Download PDFInfo
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- CN1194066C CN1194066C CNB031178723A CN03117872A CN1194066C CN 1194066 C CN1194066 C CN 1194066C CN B031178723 A CNB031178723 A CN B031178723A CN 03117872 A CN03117872 A CN 03117872A CN 1194066 C CN1194066 C CN 1194066C
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Abstract
The present invention relates to a preparation process of quasi-thin empholite rare-earth luminescent materials with crystal seeds. A stable aluminum oxide transparent colloid is prepared by taking quasi-thin empholite as a raw material, dissolving the quasi-thin empholite with water and adjusting the pH value of the solution to 1 to 4 with acid. Metal hydroxides are added to the aluminum oxide transparent colloid and are used as crystal seeds, and aluminum oxide slurry with crystal seeds is obtained by uniformly dispersing the crystal seeds in the solution. Rare-earth hydroxides are added to the aluminum oxide slurry with crystal seeds, and composite powder is obtained by drying the colloid obtained by making the aluminum oxide slurry with crystal seeds to stand. The micron order rare-earth aluminate luminescence powder material is obtained by firing the composite powder in a poor reducing atmosphere, and pulverizing and grading the composite powder. The material is prepared by a sol-gel method, so the uniformization of components is ensured. The raw materials are easily obtained, so the method is easily industrialized. The luminescence stability of the quasi-thin empholite rare-earth luminescent materials is improved by adding the hydroxides as the crystal seeds. The diffusivity of the rare earth ions is improved by adding the hydroxides of strontium, europium and dysprosium. In addition, the quasi-thin empholite rare-earth luminescent material also has the advantages of low cost, high stability, no pollution of the environment, etc. The quasi-thin empholite rare-earth luminescent material can be used as optical storage luminescent materials for various markers, decorative articles, handicraft articles, illumination devices, etc.
Description
One. technical field: luminescent ceramic material
Two. background technology: the preparation of aluminates system luminescent material is divided into high temperature solid-state method, chemical precipitation method, hydrothermal synthesis method, combustion synthesis method etc.High-temperature synthesis is present main synthetic method, promptly with Strontium carbonate powder, rare earth oxide, fusing assistant and aluminum oxide thorough mixing, burns till more than 1300 ℃ in temperature.For overcoming solid state sintering temperature height, component homogenizing problem is softened synthetic method and is obtained paying attention to.
Be called " fluorescent nanometer rare earth oxide powder and preparation method thereof " application number in name and be in 98106748.4 the patent application, method with urea chemistry and the synthetic non-doping type trivalent nano-phosphor of sonochemistry is disclosed, what adopt is the single rare earth system, does not relate to separating reuniting and dispersion technology.At document " sol-gel method rare earth ion (Gd
3+, Ho
3+, Pr
3+, Sm
3+, Dy
3+And Tm
3+) doped aluminium film [T.Ishizaka, Y.Kurokawa, Journal of Luminescence92 (2001) 57-63] " in, use AlCl
3The preparation alumina sol, the ion of about 15% high density mixes colloid.AlCl
3Introduce chlorion easily, be not easy washing, produce environmental pollution with the ammoniacal liquor peptization.
In various softening synthetic technologys, aluminate component homogenizing problem improves, but has aspect problems such as raw material sources, organic solvent, purity, complex operation, cycle length, the realization of restriction suitability for industrialized production.
The present invention adopts the pseudo-boehmite sol-gel method, by adding metal hydroxides and rare-earth hydroxide mode, addresses the above problem.
Three. summary of the invention
1. goal of the invention
The present invention adopts the pseudo-boehmite raw material, prepares the aluminates system luminescent material with sol-gel method.Use the pseudo-boehmite raw material, reduce preparation cost; Use the nano aluminium oxide colloid, impel each function ingredients homodisperse; Add aluminium hydroxide crystal seed, improve the strontium aluminate synthesis condition, improve product stability; Strontium, europium, dysprosium mix with hydroxide form, improve solid phase synthesis and rare earth ion diffusion activity.
2. technology contents
(1) technical process
Fig. 1 is a process flow sheet of the present invention.The pseudo-boehmite raw material is used water dissolution, and adjusting acidity to pH value with acid is 1-4, disperses through homogenizing, forms the aluminum oxide transparent colloid; Add metal hydroxides as crystal seed, homodisperse obtains the crystal seed alumina slurry; Add rare earth oxide again, homodisperse, the dry composite granule that gets of the colloid after leaving standstill burns till in weakly reducing atmosphere, makes rare earth aluminate luminescent powder material after pulverizing, classification.
(2) purity of pseudo-boehmite (percentage composition) is 98-99%; The solid-to-liquid ratio that is dissolved in water is an aluminum oxide: water (weight percent)=8-15%: 92-85%, adjust acidity with nitric acid or phosphoric acid, and after disperseing, homogenizing makes the aluminum oxide transparent colloid.
(3) add aluminium hydroxide and strontium hydroxide crystal seed, its purity (percentage composition) is 98-99%, median size 50～100 nanometers, in above-mentioned alumina gel, add seed crystal of aluminium hydroxide earlier, its add-on is an aluminum oxide solid content in the alumina gel: aluminium hydroxide=100: 40～60 (weight ratio), the back adds the strontium hydroxide crystal seed, and add-on is an aluminum oxide total solid content in the colloid: strontium hydroxide=100: 30～50 (weight ratio) makes the crystal seed alumina slurry after homogenizing is disperseed.
(4) rare earth luminous activator is europium hydroxide and dysprosium hydroxide, purity (percentage composition) 99.9-99.99%, median size 1-5 micron, add-on are the strontium aluminates in the slurry: the strontium aluminate in the slurry of europium hydroxide=100: 1～3 (weight ratio): dysprosium hydroxide=100: 1～3 (weight ratio) makes complex sol after homogenizing is disperseed.
(5) complex sol left standstill 12-24 hour, after temperature 80-100 ℃ of following drying removes attached water, in the presence of gac, handled 120 minutes with the 2.45GHZ microwave heating installation, and classification after the ceramic ball mill pulverizing obtains micron order strontium aluminate luminescent powder material
3. compare advantage and the positively effect that the present invention possesses with known technology
(1) uses sol-gel process, guarantee the component homogenizing, do not adopt common solid-phase synthesis to prepare strontium aluminate; (2) with the abundant pseudo-boehmite raw material of china natural resources, industrialization is easily avoided adopting aluminium-alcohol salt or al inorganic salt to prepare colloidal sol and is carried out rear-earth-doped preparation method, does not introduce foreign ion; (3) add aluminium hydroxide crystal seed, reduce γ → θ → αYang Hualv transformation temperature, improve the luminescent material product stability; (4) strontium, europium, dysprosium add with hydroxide form, strengthen homodisperse, improve the active and rare earth ion diffusion activity of strontium aluminate solid phase synthesis; (5) raw material does not have objectionable constituent, and rare earth is "dead"; (6) firing temperature is low, the aluminate product is loose, simple to operate, purity is easily controlled, the luminous intensity height.
Four. description of drawings: Fig. 1 is a process flow sheet of the present invention.
Five. embodiment
Example one: press aluminum oxide solid content in the pseudo-boehmite: water=10: 90 (percent by weight), pseudo-boehmite is dissolved in the distilled water, with percentage concentration is that to adjust pH value be=1-4 mechanical stirring 3-6 hour, to obtain transparent alumina gel for 30% nitric acid; Press aluminum oxide solid content in the colloid respectively: aluminium hydroxide=100: 50 (weight ratio), aluminum oxide total solid content: strontium hydroxide=100: 40 (weight ratio), add aluminium hydroxide crystal seed and strontium hydroxide simultaneously, median size is the 50-80 nanometer, stir after 10-12 hour, obtain the crystal seed alumina slurry; In slurry, press the strontium aluminate in the slurry: europium hydroxide=100: 1.35 adding europium hydroxides; The strontium aluminate in the slurry is pressed in the back: dysprosium hydroxide=100: 2.3 adding dysprosium hydroxides, with ceramic ball milling 10-12 hour, left standstill 24 hours, obtain gel, after 80～100 ℃ of following dryings remove attached water, in the presence of activated carbon, handled 120 minutes with the 2.45GHZ microwave heating installation, with classification after the ceramic ball mill pulverizing, obtain micron order aluminate luminescent powder material.
Example two: press aluminum oxide solid content in the pseudo-boehmite: water=14: 86 (percent by weight), pseudo-boehmite is dissolved in the distilled water, with percentage concentration is that 20% phosphoric acid is adjusted acidity mechanical stirring 5-6 hour, obtains pH value to be=the transparent alumina gel of 2-4.Press aluminum oxide solid content in the colloid: aluminium hydroxide=100: 60 (weight ratio), aluminum oxide total solid content: strontium hydroxide=100: 50 (weight ratio), strontium aluminate: rare earth=100: 2 (weight ratio), in alumina gel, add aluminium hydroxide, strontium hydroxide, europium hydroxide and the dysprosium hydroxide described in (example one) simultaneously, after ball milling 10-12 hour, left standstill 24 hours, and obtained gel.Gel temperature 80-100 ℃ of following drying in airflow removes attached water, puts into the horizontal stove, feeds 95%N
2+ 5%H
2(volume ratio) gas mixture burns till twice under temperature 1000-1200 ℃, burnt till 6-8 hour at every turn, and ceramic ball mill crushing is 1 time after burning till for twice, and sieving obtains micron order aluminate luminescent powder material.
Example three: the gel that obtains in example two carries out three times after dry 10-12 hour under temperature 80-100 ℃ and burns till in airflow, promptly in the horizontal electric furnace, feeds 70-80% (volume) N
2+ 30-20% (volume) Ar
2Gas mixture, under temperature 1200-1300 ℃, burn till, burnt till 10-12 hour at every turn, use ceramic ball mill crushing between burning till at every turn, sieving obtains micron order aluminate luminescent powder material.
Claims (2)
1, a kind of preparation technology of pseudo-boehmite crystal seed rare earth luminescent material is characterized in that technology may further comprise the steps:
1) with the pseudo-boehmite be raw material, its purity is 98-99%, is dissolved in water, and solid-to-liquid ratio is aluminum oxide: water=8-15%: 92～85%, and adjusting acidity to pH value with nitric acid or phosphoric acid is 1-4, makes the aluminum oxide transparent colloid after homogenizing is disperseed,
2) add aluminium hydroxide and strontium hydroxide crystal seed, its purity is 98-99%, median size 50-100 nanometer, in above-mentioned alumina gel, add seed crystal of aluminium hydroxide earlier, the weight ratio of add-on is an aluminum oxide solid content in the alumina gel: aluminium hydroxide=100: 40-60, and the back adds the strontium hydroxide crystal seed, and the weight ratio of add-on is an aluminum oxide solid content in the colloid: strontium hydroxide=100: 30-50, after disperseing, homogenizing makes the crystal seed alumina slurry
3) add rare earth luminous activator europium hydroxide and dysprosium hydroxide, its purity is 99.9～99.99%, median size 1-5 micron, the weight ratio of add-on is the strontium aluminate in the slurry: europium hydroxide=100: 1-3, strontium aluminate in the slurry: dysprosium hydroxide=100: 1-3, after disperseing, homogenizing makes complex sol
4) complex sol left standstill 12-24 hour, under temperature 80-100 ℃, after drying removes attached water, under the situation that gac exists, handled 120 minutes with the 2.45GHZ microwave heating installation, and classification behind the ball milling obtains micron order strontium aluminate luminescent powder material.
2, rare earth luminescent material preparation technology according to claim 1 is characterized in that homogenizing dispersion employing mechanical stirring or ceramic ball milling.
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|---|---|---|---|
| CNB031178723A CN1194066C (en) | 2003-05-13 | 2003-05-13 | Quasi-thin empholite crystal-inoculating rare earth light-emitting material preparing process |
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| CN1194066C true CN1194066C (en) | 2005-03-23 |
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| CN101928029A (en) * | 2010-09-08 | 2010-12-29 | 苏州创元投资发展(集团)有限公司 | Method for preparing aluminum oxide sol |
| CN106168552A (en) * | 2016-08-25 | 2016-11-30 | 合肥国轩高科动力能源有限公司 | Pretreatment method for measuring content of elements in boehmite |
| CN115895650B (en) * | 2022-12-30 | 2024-01-26 | 山东理工大学 | Waterproof high-temperature-resistant long-afterglow rare earth luminescent material and preparation method thereof |
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