CN1396234A - Process for preparing long-afterglow luminous alaminate powder - Google Patents
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- CN1396234A CN1396234A CN 02115979 CN02115979A CN1396234A CN 1396234 A CN1396234 A CN 1396234A CN 02115979 CN02115979 CN 02115979 CN 02115979 A CN02115979 A CN 02115979A CN 1396234 A CN1396234 A CN 1396234A
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Abstract
A process for preparing long-afterglow luminescent aluminate powder features that combination of microwave radiation technique, ultrasonic dispersion technique, and sol-gel method. Its advantages are high uniformity and small grain diameter, high speed and efficiency, and high luminescent property.
Description
Technical field
The present invention relates to long-afterglow luminous alaminate powder, comprising: long-afterglow luminescent powder and nano-aluminate luminescent powders such as strontium aluminate, barium aluminate, calcium aluminate particularly prepare the method for long-afterglow luminous alaminate powder.
Background technology
The compound formed material that makes of novel long-afterglow luminous alaminate powder and plastics is for practical, its after-glow brightness characteristic is taken out plastics kind and different, can develop at present to be used for the moulding kind as luminescent plasticss such as: crylic acid resin, polyethylene kind, polystyrene type, polypropylene-base, polycarbonate-based, ABS resin class, polyoxymethylene class and urethane.
With hybrid reactions such as novel long-afterglow luminous alaminate powder and resin, auxiliary agent and solvents, can make luminous paint, as acrylic acid or the like luminous paint and urethane noctilucence paint for lanes on highway, these coating at secure ID, false proof, indoorly fill, also there is great application prospect in field such as advertising signboard and industrial art.
In addition, also can be made into products such as fluorescent glass, luminescent enamel, luminous ornamental brick and luminous jade, these will be the frontiers that long-afterglow luminous alaminate powder is used.
Though the preparation present situation is that the high temperature solid-state method preparation method is simple at present, the product particle of producing preparation is thicker, and luminous efficiency is not high; Product purity, luminescent properties that combustion method is produced preparation are still waiting to improve; Hydrothermal synthesis method must just can carry out in the hyperbaric environment in autoclave, and the industrial production cost is higher, and the preparation material is allowed a choice, so industrial application is subjected to certain limitation; The product particle that sol-gel method makes is tiny, even; But because colloidal sol is converted into gel time and needs 50-75 hour, the production cycle is long, be unfavorable for large-scale industrialization production.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method for preparing long-afterglow luminous alaminate powder is provided, this method with short production cycle, sintering temperature is lower than high temperature solid-state method preparation temperature, and the product that makes chemistry good uniformity, particle is tiny, brightness is high, purity is high, good luminous performance.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: its method steps is:
(1) the rare-earth oxidation raw material is mixed, dissolving adds citric acid, places ultrasonic system, is mixed with glue;
(2) glue is placed the microwave synthesis system, make colloidal sol;
(3) step (2) products therefrom is placed open containers, put into the microwave synthesis system again, make xerogel;
(4) drying;
(5) step (4) products therefrom is placed chamber type electric resistance furnace, remove organic matter, prepare the intermediate in the nanoscale scope at cold condition;
(6) step (5) products therefrom is placed nitrogen hydrogen High Temperature Furnaces Heating Apparatus, feed hydrogen, calcination under hot conditions;
(7) step (6) products therefrom being carried out ultrasonic wave embathes:
(8) will prepare product separates dry;
(9) pulverize finished product.
The present invention prepares production technique in conjunction with supersonic method, sol-gel method integrated application in preparing, produce long-afterglow luminous alaminate powder, optimizing with microwave method, has opened up new approach.Transform to gel at colloidal sol, Drying of gels in the technological processs such as crystallization, adopts microwave irradiation technology, and closely in conjunction with the ultrasonic dispersing technology; In technological process, prepared the intermediate in the nanoscale scope that is evenly distributed, made rare earth ion uniform distribution in system.Novel process of the present invention has promptly kept the advantage that sol-gel method products obtained therefrom particle diameter is little, be evenly distributed, and utilizes quick, the efficient characteristics of microwave method again, has shortened the whole process of preparation time greatly, effectively prevents that preparation process middle-weight rare earths ion from forming cluster simultaneously; Prevent that effectively the product particle from forming reunion, make the product particle keep tiny even, improved luminescent properties significantly.
Description of drawings
Fig. 1 is an embodiment of the invention schema
After Fig. 2 is the differing temps sintering, the powder crystal diffractogram of gained twinkler
Fig. 3 determines the best proportioning figure of Eu/Sr
Fig. 4 is for determining microwave best heat-up time of figure
Fig. 5 is 100,000 times of TEM bright field images of the intermediate in the nanoscale scope of the present invention's preparation
Fig. 6 prepares 10,000 times of TEM bright field images that product is the nano-aluminate luminescent powder for the present invention
Fig. 7 prepares the X ray powder crystal diffractogram of product for the present invention
The three dimension scanning orthographic plan of Fig. 8 product luminescent properties
The three dimension scanning stereographic map of Fig. 9 product luminescent properties
The emission wavelength scintigram of Figure 10 product
The excitation wavelength scintigram of Figure 11 product
Specific embodiments
As shown in Figure 1, production craft step of the present invention is: take by weighing Strontium carbonate powder SrCO by certain stoichiometric ratio
3(AR) be 1.058 kilograms, aluminum nitrate Al (NO
3)
39H
2O (AR) is 3.751 kilograms, europiumsesquioxide Eu
2O
3(99.99%) is 0.008 kilogram, Dysprosium trioxide Dy
2O
3(99.99%) is 0.028 kilogram, adds 18.75 liters of distilled water.With SrCO
3, Al (NO
3)
39H
2O (AR), Eu
2O
3, Dy
2O
3Mixed, add 4.3 liters of 1: 1 nitric acid.Under condition of normal pressure, regulating and controlling temperature is 50 ℃-95 ℃, and then adds 7.932 kilograms of citric acids, is prepared into glue and places ultrasonic equipment.The ready-formed glue is placed microwave synthesis system (MMR-12MicroSYNTH), and design effort condition and working routine under the condition of condensing reflux, make it to make colloidal sol 60 ℃-95 ℃ reactions down.After reaction finished in the microwave synthesis system, the colloidal sol with reaction under condition of normal pressure placed open containers, and then puts into microwave oven and heat, and was controlled to be low fiery small power, made xerogel.The xerogel that makes is placed far infrared drying oven, the regulation and control suitable temp, remove moisture content, to put into chamber type electric resistance furnace after the dried product ball mill pulverizing, make it at 200 ℃ of-900 ℃ of constant temperature of lesser temps, remove organic matter, preparation nanostructure intermediate (the average grain yardstick is 20nm, sees Fig. 5).The taking-up of nanostructure intermediate after the low-temperature heat treatment is cooled to room temperature, adds 1.2 kilograms of boric acid (HBO
3) and make it to mix after, put into nitrogen hydrogen High Temperature Furnaces Heating Apparatus.Regulate H
2(the stream amount starts working routine, is controlled at the 1%-9% scope, at 600 ℃ of-1300 ℃ of following calcination samples of hot conditions.Product behind the high temperature sintering is placed ultrasonic system 2min-20min and add dispersion agents such as ethanol, reach discrete particles, the purpose of modification of surfaces.The preparation product that will embathe is separated, and it is dry to put into loft drier, removes unnecessary dispersion agent.Product is carried out comminution by gas stream, and it is soft-agglomerated to utilize the elasticity air-flow to eliminate the product that causes in the production process.Just obtain alumine acid strontium long afterglow luminescent powder (the average grain yardstick is 100nm, sees Fig. 6).According to different stoichiometrics, use prepared production process of the present invention and method thereof, can obtain calcium aluminate, barium aluminate long-afterglow luminescent powder respectively equally.
1, high temperature solid-state method prepares the calcination temperature of product:
According to materialogy and SrO-Al
2O
3System phase diagram can be learnt, if adopt high temperature solid-state method directly to carry out sintering, expect single-phase component S rOAl
2O
3Must be by the stoichiometric ratio batching, being heated to more than 1790 ℃ becomes liquid phase, is cooled to single-phase SrOAl then gradually
2O
3Crystal.And former research also shows, because single-phase SrOAl
2O
3High-melting-point, the preparation SrOAl
2O
3: Eu
2+, (Dy
3+) during the steady persistence body, needing to solve the pyritous problem, this is just to the very high requirement of equipment proposition.
2, calcination process summary: the SrOAl that the microwave synthesis system is made
2O
3: Eu
2+And SrOAl
2O
3: Eu
2+, (Dy
3+) xerogel put into crucible and insert stove, be warmed up to 600 ℃ from room temperature, be incubated 4h then, naturally cooling in the stove, after cooling, xerogel becomes white powder, takes by weighing a certain amount of powder then, adds certain amount of H
3BO
3As fusing assistant, grinding is evenly mixed, is placed in the corundum container.For preventing that at high temperature rare earth ion is oxidized to high valence state, ammonia decomposes hydrogen and uses mainly as reducing atmosphere.Sample is placed sintering under the differing temps, determine optimal sintering temperature at last.Fig. 2 is the twinkler XRD powder diagram of (insulation 2h) under the different calcining temperatures.As can be seen from Figure 2, sample mainly is SrCO after 600 ℃ and the 800 ℃ of calcinations
3Phase; And just begin to occur twinkler Sr behind 960 ℃ of following calcination 2h
5Al
8O
17And Sr
3Al
2O
6Biphase mixes; Substantially be Sr in the twinkler behind the calcination 6h
3Al
2O
6And SrAl
2O
4Phase.
This explanation promptly begins to form SrAl at 960 ℃
2O
4, 1050 ℃ have been essentially SrAl
2O
4Phase goes up basic not change, is still SrAl for 1150-1400 ℃
2O
4
Analyze explanation increasing and increasing, SrO-Al from Fig. 2 along with sintering temperature and time
2O
3System is changed mutually by the rich in opposite directions aluminium of rich strontium, changes the SrAl2O4 phase fully at 1050 ℃.Consider from time of persistence and afterglow intensity composite factor, determine that microwave-sol-gel method makes best calcination junction temperature behind the xerogel in 1200-1250 ℃ of scope, compare for 1790 ℃ with the high temperature solid-state method calcination temperature, calcination temperature has descended 500 ℃.
3, in microwave-Prepared by Sol Gel Method, the determining of the best proportioning of Eu/Sr:
In microwave-Prepared by Sol Gel Method, under the identical situation of other conditions, when the ratio Eu/Sr=0.3% according to amount fed intake, the long afterglow powder that obtains was luminous the strongest.(see figure 3)
4, microwave heating time determines
In microwave-Prepared by Sol Gel Method, when other situations were identical, microwave best heat-up time was 155 minutes, the maximum (see figure 4) of relative luminous intensity.Microwave-Prepared by Sol Gel Method time be 2.5 hours be to compare in 72 hours with the thermostatic water-bath method preparation time, the time of producing the long-persistence luminous body product of preparation has shortened 28 times.
With microwave-sol-gel method synthetic intermediate mean particle size is the 20nm (see figure 5), and the mean particle size of synthetic product can reach the 100nm (see figure 6).The X powder crystal diffractogram of preparing product shows that the preparation product is SrAl
2O
4: Eu
3+, Dy
3+(see figure 7).The luminescent properties of preparing product detects and shows luminescent properties good (seeing Fig. 8, Fig. 9, Figure 10, Figure 11).
Claims (10)
1, a kind of method for preparing long-afterglow luminous alaminate powder, it is characterized in that: its method steps is:
(1) the rare-earth oxidation raw material is mixed, dissolving adds citric acid, places ultrasonic equipment, is mixed with glue;
(2) glue is placed the microwave synthesis system, make colloidal sol;
(3) step (2) products therefrom is placed open containers, put into the microwave synthesis system again, make xerogel;
(4) drying;
(5) step (4) products therefrom is placed chamber type electric resistance furnace, remove organic matter, prepare the intermediate in the nanoscale scope at cold condition;
(6) step (5) products therefrom is placed nitrogen hydrogen High Temperature Furnaces Heating Apparatus, feeds hydrogen, calcination under hot conditions:
(7) step (6) products therefrom being carried out ultrasonic wave embathes;
(8) will prepare product separates dry;
(9) pulverize finished product.
2, the method for claim 1 is characterized in that: will add 1: 1 nitric acid in the rare-earth oxidation raw material.
3, the method for claim 1 is characterized in that: in the step (1), place ultrasonic system, under condition of normal pressure, glue preparation temperature is controlled at 50 ℃-95 ℃.
4, the method for claim 1 is characterized in that: in the step (2), the glue for preparing is placed the microwave synthesis system, under the condensing reflux condition, controlled temperature is 60 ℃-95 ℃, makes colloidal sol.
5, the method for claim 1 is characterized in that: in the step (3), microwave heating power is controlled at low fiery power under normal pressure.
6, method according to claim 1, it is characterized in that: in the step (5), the cold condition temperature is at 200-900 ℃.
7, the method for claim 1 is characterized in that: in nitrogen hydrogen High Temperature Furnaces Heating Apparatus, the percentage composition that ammonia decomposes hydrogen is controlled at the 1%-9% scope.
8, method according to claim 1, it is characterized in that: the high-temperature roasting temperature is at 1200 ℃-1250 ℃.
9, method according to claim 1, it is characterized in that: the ultrasonic wave time of embathing was controlled at 2-20 minute.
10, method according to claim 1 is characterized in that: the pulverizing of step (9) adopts airflow milling to pulverize.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301274C (en) * | 2005-05-25 | 2007-02-21 | 北京阿格蕾雅科技发展有限公司 | Method for preparing illuminant organic glass in long persistence, and organic glass prepared by the method |
| CN1306005C (en) * | 2004-11-15 | 2007-03-21 | 王兵 | Aluminate-base rare earth long afterglow luminous material synthesizing method |
| CN100395307C (en) * | 2004-10-13 | 2008-06-18 | 孙家跃 | Sol-foaming process for preparing powder material in steady persistance without ball milling |
| CN101386784B (en) * | 2008-09-05 | 2013-06-26 | 陈哲 | Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion |
| CN104119874A (en) * | 2013-04-26 | 2014-10-29 | 海洋王照明科技股份有限公司 | Strontium aluminate luminescent material and preparation method thereof |
| CN104119872A (en) * | 2013-04-26 | 2014-10-29 | 海洋王照明科技股份有限公司 | Hollow-structure strontium aluminate luminescent material and preparation method thereof |
| CN104609894A (en) * | 2014-12-17 | 2015-05-13 | 高炳申 | Superlong afterglow luminous pebble and preparation method thereof |
| CN109851260A (en) * | 2019-01-18 | 2019-06-07 | 武汉科技大学 | A kind of carbon containing aluminous cement and preparation method thereof |
-
2002
- 2002-06-14 CN CNB021159793A patent/CN1159411C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395307C (en) * | 2004-10-13 | 2008-06-18 | 孙家跃 | Sol-foaming process for preparing powder material in steady persistance without ball milling |
| CN1306005C (en) * | 2004-11-15 | 2007-03-21 | 王兵 | Aluminate-base rare earth long afterglow luminous material synthesizing method |
| CN1301274C (en) * | 2005-05-25 | 2007-02-21 | 北京阿格蕾雅科技发展有限公司 | Method for preparing illuminant organic glass in long persistence, and organic glass prepared by the method |
| CN101386784B (en) * | 2008-09-05 | 2013-06-26 | 陈哲 | Method for synthesizing nano fluorescent powder by microwave excited low-temperature liquid phase combustion |
| CN104119874A (en) * | 2013-04-26 | 2014-10-29 | 海洋王照明科技股份有限公司 | Strontium aluminate luminescent material and preparation method thereof |
| CN104119872A (en) * | 2013-04-26 | 2014-10-29 | 海洋王照明科技股份有限公司 | Hollow-structure strontium aluminate luminescent material and preparation method thereof |
| CN104119872B (en) * | 2013-04-26 | 2016-08-10 | 海洋王照明科技股份有限公司 | A kind of strontium aluminate luminous material of hollow structure and preparation method thereof |
| CN104609894A (en) * | 2014-12-17 | 2015-05-13 | 高炳申 | Superlong afterglow luminous pebble and preparation method thereof |
| CN109851260A (en) * | 2019-01-18 | 2019-06-07 | 武汉科技大学 | A kind of carbon containing aluminous cement and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1159411C (en) | 2004-07-28 |
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