CN1923947B - Method for preparing spherical rare earth red phosphor particle by droplet-particle transform - Google Patents
Method for preparing spherical rare earth red phosphor particle by droplet-particle transform Download PDFInfo
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- CN1923947B CN1923947B CN2005101376338A CN200510137633A CN1923947B CN 1923947 B CN1923947 B CN 1923947B CN 2005101376338 A CN2005101376338 A CN 2005101376338A CN 200510137633 A CN200510137633 A CN 200510137633A CN 1923947 B CN1923947 B CN 1923947B
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Abstract
The invention provides a method for preparing spherical rare earth red phosphor particle by droplet-particle transform, comprising: a step of preparing initiation materials with metal ion concentration of 0.005M to 2.0M by adding acid into rare earth oxides; a carbamide mixing step of adding carbamide into the initiation materials and mixing; a liquid drop forming step of forming liquid drops by spraying or atomizing using ultrasonics; a drop-particle transforming step comprising evaporating, drying and pyrogenation; and a powder forming step including cleaning, drying the processed particles.
Description
Technical field
The present invention relates to a kind of the conversion and prepare spherical rare earth red phosphor particulate method by droplet-particle, more specifically, relate to by rare-earth oxide is mixed with various acid, in mixture, add urea subsequently, produce drop by mixture, with drop through pervaporation, drying, pyrolysis and washing to obtain oxide phosphor, then with the oxide phosphor thermal treatment and the washing that obtain, thus the spherical rare earth red phosphor particulate method of the preparation oxide compound of preparation spherical phosphor particles.
Background technology
Rare earth element is meant and comprises except scandium (Sc, ordination number 21) and actinium (Ac, ordination number 89) in addition, 15 kinds of elements that belong to the 3A family of the periodic table of elements, for example yttrium (Y, ordination number 39) and comprising from lanthanum (La, ordination number 57) to lutetium (Lu, ordination number 71) lanthanon, but do not comprise the promethium (Pm, ordination number 61) that is present in occurring in nature hardly.Yet in these elements, lanthanum in the earth's crust of the earth (La) and cerium (Ce) are abundanter than antimony (Sb), and in the earth's crust of the earth, except lutetium (Lu), other element exists with the amount similar to the amount of silver (Ag) or tungsten (W), and these elements are also referred to as lanthanon.Rare earth ore is that the by product as other main ore obtains, thereby the price of rare earth ore and output greatly depend on the market requirement of main ore.
Along with recent industrial expansion, rare earth metal and matrix material little by little are used to various application as the hi-tech material, therefore as Electrical and Electronic, catalyzer, optics, polishing material, permanent magnet, specific alloy and phosphorescent substance, and face the needs of growth at full speed.Domestic rare-earth industry has covered very limited range of application, and its major part is the preparation of phosphorescent substance, rumbling compound, cubic zirconia stablizer and glassmaker's soap etc., and other application simultaneously is still under development.
Current trend is that our daily life is shown device fully and surrounds, and comprises the terminal of various mobile telephones, MP3 player, notebook computer, TV, PC indicating meter, diagnostic device and vehicle remote information processing.Some representational display unit comprises by the plasma display that becomes focus recently, and Field Emission Display (FEDs) is the flat-panel monitor of representative.Wherein, plasma display panel (PDPs) has the powerful advantages as screen sizes and high image quality to realization digital picture key, and has wide visual angle.Thereby, in some developed country, comprising the U.S. and Britain, the competition between commercial enterprise is recently just becoming fiercer to occupy the market that produces with digital TV broadcasting earlier, and PDPs is just causing than bigger before concern.
Phosphorescent substance is to absorb to cause that electronics enters excited state and returns the ground state and the luminescent material of the various external energies of visible emitting mainly then, and they have been used as and show materials of different colors in the display unit.Particularly in PDPs,, thereby must develop heat-resistant oxide phosphorescent substance with chemical affinity big between element, excellent durability and high photoluminescence efficiency by vacuum ultraviolet ray (VUV) excitation phosphor of noble gas discharge generation.Current, known most of oxide phosphor prepares by solid phase synthesis process.The shortcoming of tradition solid phase synthesis process is to be difficult to control particle and configuration of surface, because might mix impurity in the process of blending ingredients, and high-temperature heat treatment is necessary.In order to address these problems, various liquid and gas synthetic methods have been developed so that the preparation spheroidal particle becomes possibility.Yet the liquid phase process of implementing in batch system still need improved aspect productive rate and the production cost; And gas phase process allows preparation high purity particle, unlike the situation in the liquid phase process, all different and complicated technology, chemical substance and the preparation condition according to the particle needs that will prepare, therefore, regardless of the grain type that will prepare, this method all can be implemented as preparation particulate ordinary method.Yet the particle for preparing by gas phase process is in the very hypersaturated state of height, wherein be difficult to control nucleation rate, and the particle that obtains is the particle of a large amount of nano-scales.The particulate of the nano-scale that these are a large amount of is characterised in that to have very high surfactivity and obtain with high state of aggregation.Therefore, obtain particle with the second particle with fragile structures of state of aggregation, rather than obtain with spherical primary particle.Therefore, the shortcoming of gas phase process is still to be difficult to control simply the particle performance that obtains.On the contrary, transform preparation particulate method by droplet-particle and so be implemented, drop plays the effect that a kind of all reactions are defined to its inner microreactor,, therefore the final form of particulate that obtains is for spherical, and the form of itself and droplet is similar.And then if the size of drop can be controlled as single dispersion in spray process, then final particulate dispersity can reach very narrow.Therefore, be suspended with the related transformation that takes place owing to the enforcement of droplet-particle method for transformation depends on drop in gas, this method possesses whole advantages of liquid phase process and gas phase process, and further has the synergy of these beneficial effects.When phosphorescent substance was sphere, the scattering of light on particle surface can reduce, and when phosphorescent substance mixes with tackiness agent, can make the paste of good order and condition.Thereby expection can prepare good phosphorus membrane.
Viewpoint thus, Korean Patent has been described for No. 371053 by spray pyrolysis preparation to be had uniform-dimension and shape and has the exploitation of method of the oxide phosphor of splendid photoluminescence performance, wherein proposes by using spray pyrolysis to prepare spherical phosphorescent substance.Yet, have the structure of hollow by the phosphor powder of spray pyrolysis preparation, thereby the particulate sphere is destroyed in the required postheat treatment technology of the photoluminescence performance that improves phosphorescent substance, causes undesirable particulate vesicular structure.In addition, although the particulate form that control obtains by spray pyrolysis in the application of phosphorescent substance evenly is necessary, the routine techniques that is used for controlling particle form that is proposed at spray pyrolysis, for example the technology of the size of the technology of the concentration of conditioned reaction solution, the drop that regulate to produce, regulate the technology of product temperature etc., all be industrial infeasible.Also be not easy to derive for reaching the spherical required working condition of homogeneous, and the condition of deriving is inapplicable very in practice.
In addition, the patent application of Korea S's not substantive examination as yet proposes for 2001-2822 number to use strainer expansion aerosol generator (filter expansion aerosol generator (FEAG)) or ultrasonic spray pyrolysis device to prepare the method for oxide phosphor by spray pyrolysis, wherein at first prepare the colloidal solution that is used for spray pyrolysis as reaction soln, this solution is sprayed into tiny drop, and prepares microparticle by dry and pyrolysis.The key of the method that is proposed is to prepare colloidal solution as starting raw material, but the shortcoming of this method is, even the form that the structure of being set up by perfect colloid can keep granule interior to be filled can not guarantee the homogeneity of colloidal solution.
Therefore, need a kind of technology of exploitation, wherein using spray pyrolysis to prepare in the multi-component oxide phosphorescent substance process, the particulate form can and remain sphere well by control equably, and can obtain the oxide phosphor that is easy to process.
Summary of the invention
In order to address the above problem, an object of the present invention is to provide a kind of preparation spherical rare earth red phosphor particulate method, this particle can be used for various application and has 0.5 μ m to the size less than 2 mu m ranges, and granule interior is filled equably.
Another object of the present invention provides the method that droplet-particle transforms, and can prepare a large amount of spherical rare earth red phosphor particles in enormous quantities by this method.
Another purpose of the present invention provides a kind of preparation method, and in the method, with respect to the ordinary method of using the SILVER REAGENT rare-earth salts, by it directly being dissolved in use rare earth oxide in back in the acid, technology is more perfect and more convenient.
To achieve these goals, the invention provides by droplet-particle and transform the method that prepare the spherical rare-earth phosphor particles, this method comprises add the starting raw material preparation process of acid with the starting raw material for preparing the rare earth ion concentration that has 0.005M～2.0M scope respectively in rare earth oxide; The urea mixing step that in starting raw material, adds urea; Mixture forms step through supersonic spraying with the drop that forms drop; Droplet-particle the step of converting of evaporation, drying and pyrolysis drop; With washing and dry through pervaporation, drying and pyrolytic particulate powder formation step.
The present invention also provides a kind of method, after it selectively is included in powder formation step, makes the powder that obtains improve step through Overheating Treatment, washing and exsiccant degree of crystallinity.
The present invention also provides a kind of method, and wherein the urea that uses in the urea mixing step is mixed with powdered form, and the starting raw material of relative 100 weight parts, is added into the amount of 1～10 weight part.
The present invention also provides a kind of method, wherein in droplet-particle step of converting, evaporation is carried out at 100～300 ℃, and drying is carried out at 400～600 ℃, and pyrolysis is carried out at 700～1000 ℃, so evaporation, drying and pyrolytic process are to need not repetition in sequence.
The present invention also provides a kind of method, and wherein in droplet-particle step of converting, drop is processed with the speed of 1～9L/min.
The present invention also provides a kind of method, and wherein improve the spherical rare-earth phosphor particles for preparing in the step in degree of crystallinity and be formed powder, with spherical phosphor particles with respect to 100 weight parts, the Neutral ammonium fluoride (NH of the amount of 5～20 weight parts
4F) mix, in the calcining furnace of 900～1600 ℃ of air atmospheres, heat-treated then 30 minutes～6 hours.
Description of drawings
Fig. 1 prepares the schema of the method for spherical phosphor particles for showing a technical scheme according to the present invention;
Fig. 2 transforms the synoptic diagram of the pyrolysis installation of preparation spherical phosphor particles by droplet-particle according to a technical scheme of the present invention for expression;
Fig. 3 transforms the spherical rare-earth particulate scanning electron photomicrograph of preparation for what take by droplet-particle according to a technical scheme of the present invention before washing, drying and thermal treatment particle;
Fig. 4 takes the spherical rare-earth particulate scanning electron photomicrograph of Fig. 3 for the particle process in 1000 ℃ of thermal treatments 2 hours, washing and dry back;
Fig. 5 is for when starting material concentration is 0.1M, according to the scanning electron photomicrograph of the spherical phosphor particles of a technical scheme of the present invention;
Fig. 6 is for when starting material concentration is 2.0M, according to the scanning electron photomicrograph of the spherical phosphor particles of a technical scheme of the present invention;
Fig. 7 is for when flow rate of carrier gas becomes 1L/min, according to the scanning electron photomicrograph of the spherical phosphor particles of a technical scheme of the present invention;
Fig. 8 is for when flow rate of carrier gas becomes 9L/min, according to the scanning electron photomicrograph of the spherical phosphor particles of a technical scheme of the present invention;
Fig. 9 is the scanning electron photomicrograph according to the spherical phosphor particles of a technical scheme of the present invention, and this particle obtains through reaction by the urea of adding in starting raw material and dissolving 0.5M and with mixture;
Figure 10 is according to one embodiment of the invention, and contrast does not add urea and the spherical phosphor particles that obtains and by adding and dissolving 0.5M urea and make the figure of the photoluminescence intensity of the spherical phosphor particles that mixture obtains through reaction in starting raw material in starting raw material;
Figure 11 is for taking after increasing step through degree of crystallinity at particle, according to the scanning electron photomicrograph of the spherical phosphor particles of one embodiment of the invention; With
Figure 12 is according to one embodiment of the invention, and contrast does not add Neutral ammonium fluoride and the spherical phosphor particles that obtains and add the Neutral ammonium fluoride of 10,20 and 30 weight parts respectively and the figure of the photoluminescence intensity of the spherical phosphor particles that obtains in thermal treatment.
Reference numeral
100: the carrier gas supply
200: under meter
300: starting raw material
400: ultra-sonic generator
500: tubular reactor
510,520,530: the first chambers, second chamber, the 3rd chamber
600: electric furnace
700: particle collector
800: gas treatment equipment
Embodiment
Hereinafter, will describe the preferred embodiments of the invention in detail with reference to the accompanying drawings.At first, it should be noted that under all possible situation, assembly or element identical in the accompanying drawing are represented by identical Reference numeral.In describing the present invention, omit detailed description to relevant known function or structure to avoid main points of the present invention ambiguous.
Fig. 1 prepares the schema of the method for spherical phosphor particles for showing an optimal technical scheme according to the present invention; And Fig. 2 transforms the synoptic diagram of the pyrolysis installation of preparation spherical phosphor particles by droplet-particle according to a technical scheme of the present invention for expression;
Transform the method for preparing spherical phosphor particles according to the preferred embodiments of the invention by droplet-particle, can comprise in rare earth oxide, adding the starting raw material preparation process of acid with the preparation starting raw material; The urea mixing step that in starting raw material, adds urea; Form the step of drop by mixture; Droplet-particle the step of converting of evaporation, drying and pyrolysis drop; Form step with after scouring and dry evaporation, drying and pyrolytic particulate powder, and selectively, make the powder that obtains improve step through Overheating Treatment, washing and exsiccant degree of crystallinity.
Starting raw material can be by adding for example nitric acid (HNO in rare earth oxide
3) acid with dissolved oxygen thing in acid, and add deionized water and prepare to obtain suitable concentration.Preferably, fully stir down, rare earth oxide is dissolved in the nitric acid fully, add deionized water then to regulate Y by according to stoichiometric ratio
3+And Eu
3+Concentration be that 0.005M～2.0M obtains starting raw material.In limited time concentration is too low when concentration is lower than 0.005M following, that is, the amount of solute (amount of salt) very little, so productive rate step-down.When concentration is higher than going up in limited time of 2.0M, then in the process of ullrasonic spraying, obtain relatively poor spraying, and become and be difficult to collecting granules.
When Fig. 5 and Fig. 6 are 0.1M and 2.0M for changing starting material concentration respectively, the scanning electron photomicrograph of the spherical phosphor particles that obtains.From Photomicrograph as can be seen, higher concentration causes bigger particle size.As can be seen, when concentration increased, the amount of the salt in the drop increased, and the size of droplet also increases, and therefore final particle size also increases.Even under high relatively 2.0M concentration, it is spherical that particle keeps.Yet, be higher than the concentration of 2.0M, obtain relatively poor spraying.
After this, starting raw material mixes with urea, and this urea is mixed with powder type and the starting raw material of relative 100 weight parts, is added into the amount of 1～10 weight part.When urea is added into the amount that is lower than lower limit 1 weight part, then can not obtain required spherical phosphor particles.When urea was added into the amount greater than the upper limit 10 weight parts, urea components may be bonded on the particle surface and reduce photoluminescence brightness.
Under special frequency band (1.67MHz) effect that produces by ultra-sonic generator 400, form the drop of the mixture that contains starting raw material and urea.The various technology that increase the drop amount that produces are arranged, comprise and use ultrasonic nozzle, two-fluid spraying etc.Yet these technology there is no too big advantage in yield aspects because the drop that produces is excessive dimensionally, so the concentration of starting raw material should be provided with relatively low to obtain small sized particles.Thereby it is preferred producing the ullrasonic spraying with 5～20 μ m size drops.Simultaneously, ultra-sonic generator 400 is connected in cylinder 100 in the left side, is useful in this cylinder by under meter 200, and mixture droplets is sent to the carrier gas of high-temperature tubular reactor 500, for example nitrogen (N
2) or air.
Fig. 3 transforms the spherical rare-earth particulate scanning electron photomicrograph of preparation for what take before washing, drying and thermal treatment at particle by droplet-particle.
The mixture that transmits is converted into particle by evaporation, drying and pyrolysis in reactor 500.Mixture and carrier gas are introduced in the reactor of being made up of the concentric tube of quartz manufacturing 500.Reactor 500 can be made of three chambers, and it is used for evaporation, drying and pyrolysis respectively under proper condition.Preferably, first chamber 510 is at 100～300 ℃, and second chamber 520 at 700～1000 ℃, need not repetition at 400～600 ℃ and the 3rd chamber 530 so evaporation, drying and pyrolysis can be carried out continuously.
Mixture can be processed with the speed of 1～9L/min in reactor 500.When mixture is processed with the speed that is lower than 1L/min, particle may be in reactor advantageously through suitably handling fully, but low speed can cause the problem of productivity.But when this process was carried out with the speed that surpasses 9L/min, the drop treatment process by drying etc. may not suitable carrying out.
Fig. 7 and Fig. 8 are for being 1L/min and 9L/min by changing flow rate of carrier gas respectively, and the scanning electron photomicrograph of the spherical phosphor particles of preparation.Flow rate of carrier gas greatly depends on drop and rests on residence time in the reactor.As can be seen from the results, when flow velocity was 9L/min, coating of particles was by havoc and macrobead occurs.This is considered to because the high flow rate of carrier gas causes drop short residence time in chamber in reactor, and thereby drop may pass through sufficient evaporation, drying and pyrolysis or may pass through aforesaid process with repetitive mode.In addition, around reactor 500 horizontal pipe 600 is arranged, this horizontal pipe is to the each several part of reactor, that is, first chamber to the, three chambers provide an amount of heat.
The drop of mixture is converted into the rare earth particle and is filtered then, and filtration procedure is to carry out in the collector 700 of the end that is arranged at reactor 500.This collector 700 links to each other with the thermal glass cup, and is inserted with the O-ring between two cups.Particle by preparing for 1～5 time with deionized water wash under the stirring of magnetic agitation is collected by filtration unit subsequently then, and is dry with the spherical red phosphor particles of final formation powdery in loft drier then.
Simultaneously, collection is by behind the particle of high-temperature tubular reactor 500, and solvent is from wherein removing, and before being emitted, carrier gas and residual material unreacted and that produce are neutralized in the gas treatment equipment 800 that contains sodium hydroxide (NaOH) solution.
Fig. 4 takes the spherical rare-earth particulate scanning electron photomicrograph of Fig. 3 for the particle process in 1000 ℃ of thermal treatments 2 hours, washing and dry back.Two photos all show the sphere that particle remains intact, and particularly, even after thermal treatment, also do not observe agglomeration of particles.
According to another embodiment of the present invention, when in reactor, spherical phosphor particles with repetitive mode through after pervaporation, drying and the pyrolytic process or under relative low temperature when synthetic, may further include the additional thermal treatment process that causes crystallization and improve brightness, to improve particulate degree of crystallinity.Particularly, when the spherical rare-earth phosphor particles of preparation forms powder, the spherical phosphor particles of relative 100 weight parts, the Neutral ammonium fluoride (NH of the amount of adding 5～20 weight parts
4F).Subsequently, spherical phosphor particles can be under air atmosphere thermal treatment 30 minutes to 6 hours in 900～1600 ℃ the calcining furnace, subsequently with deionized water or alcohol washing, and filter then and dry.The material that can be used to additional degree of crystallinity raising step is not limited to Neutral ammonium fluoride, but this material should have fast relatively at low temperatures velocity of evaporation, that is, this material should have low fusing point, although and it is helpful to crystallization, this material should not influence the primitive reaction material.When the amount of substance that adds less than 5 weight parts, then to improve effect not remarkable for degree of crystallinity.When the amount of substance that adds greater than 20 weight parts, then observe the particle of a large amount of breakages, and this is considered to because improve the damage that the volatilization of the material of degree of crystallinity causes particle surface.
Embodiment 1
112.9g Y
2O
3Little by little added 2000mL nitric acid (HNO is housed
3) beaker in dissolved oxygen thing therein.At this, because violent reaction may take place, oxide powder is added into the amount of adjusting carefully.When mild heat mixture and slow the stirring, mixture becomes settled solution.In this settled solution, add deionized water with the cumulative volume to 1 of adjusting solution liter, and Y in this moment solution
3+Concentration be 0.5M.Add the nitric acid of the minimum of dissolved oxygen thing fully.The Eu of 176g
2O
3Dissolved with above-mentioned same way as, and the cumulative volume of solution is adjusted to 1 liter to obtain containing 0.5M Eu
3+Solution.By in yttrium solution, adding the Eu of 3～10 weight percents
2O
3Thereby preparation starting raw material.
By ultrasonic nebulizer prepared starting raw material is converted into the drop with tens of micron-scales, and by the nitrogen as carrier gas, drop is transferred to the high-temperature tubular reactor.The high-temperature tubular reactor is through gradually temperature variation, thereby can sequentially realize evaporation, drying and the pyrolysis of drop.That is, because the evaporation in the drop occurs in the inlet part that drop is introduced into, inlet keeps low relatively temperature, for example 300 ℃; The interior solute exsiccant next section of drop takes place be maintained at 600 ℃; And final, drop pyrolytic next section taking place be maintained at 1000 ℃, thereby allows sufficient reacting to carry out.Here, nitrogen flow rate is 3L/min.And the spherical phosphor particles of in collector collecting resulting with deionized water wash 1～5 time filtered in filtration unit with film filter, and be dry in moisture eliminator then.
The powder that obtains after the drying is thermal treatment 2～3 hours in calcining furnace under the air atmosphere in 900～1200 ℃ temperature range.The particle that obtains after the thermal treatment also washs 2～3 times fully with deionized water, filters in filtration unit with film filter, and is dry in moisture eliminator then.
Embodiment 2
Prepare the spherical rare-earth powder with embodiment 1 identical method, except stir down to starting raw material add urea to the concentration of 0.5M being dissolved in the starting raw material, and mixture is through beyond the prepared in reaction powder.
Fig. 9 is by the urea of dissolving 0.5M in starting raw material and makes mixture through reacting the scanning electron photomicrograph of the spherical phosphor particles that obtains.Shown in Photomicrograph, the spherical morphology of spherical phosphor particles with do not add the particulate plesiomorphism that urea obtains, but do not observe the particle of a large amount of disruptive particles or hollow in this example.
Figure 10 is for the demonstration spherical phosphor particles that adding urea does not obtain in starting raw material with by dissolving 0.5M urea and make the mixture process react the figure of the photoluminescence intensity of the spherical phosphor particles that obtains in starting raw material.As can be seen from the results, two groups of spherical phosphor particles all show the strongest emmission spectrum at the wavelength 612nm place of corresponding red light photoluminescence, and, show the photoluminescence intensity of raising by the spherical phosphor particles that adds urea production with respect to the spherical phosphor particles that does not add urea production.Can believe that the quantity of break particle or hollow particle can reduce when adding urea, and thereby improve photoluminescence performance.
Embodiment 3
Prepare the spherical rare-earth powder with embodiment 1 identical method, except the Neutral ammonium fluoride (NH of 10 weight parts before the thermal treatment of calcining furnace
4F) mix fully with phosphor powder, then mixture at 1000 ℃ beyond thermal treatment 2 hours.
Figure 11 is the scanning electron photomicrograph of the spherical phosphor particles that obtains in embodiment 3.Shown in Photomicrograph, Neutral ammonium fluoride does not have remarkable influence to the form of spherical phosphor particles, and the particle of preparation keeps non-accumulative sphere.
Figure 12 does not add Neutral ammonium fluoride (NH for being illustrated in the thermal treatment
4F) spherical phosphor particles that obtains and add the Neutral ammonium fluoride of 10,20 and 30 weight parts respectively and the figure of the photoluminescence intensity of the spherical phosphor particles that obtains.As can be seen from the results, the spherical phosphor particles that obtains with respect to not adding Neutral ammonium fluoride is by adding the Neutral ammonium fluoride (NH of 10 weight parts
4F) spherical phosphor particles that obtains shows the photoluminescent property that improves.
Embodiment 4
Prepare the spherical rare-earth powder with embodiment 2 identical methods, except the Neutral ammonium fluoride (NH of 10 weight parts before the thermal treatment of calcining furnace
4F) mix fully with phosphor powder, and make mixture through Overheating Treatment.
According to the preparation spherical rare-earth phosphor particulate method of the embodiment of the invention described above,, has the remarkable inhomogeneity effect of improving spherical phosphor particles by adding urea to cause the even filling of granule interior.
Further, the invention has the advantages that because progressively thermal treatment allows to remove element unnecessary in each step, so the preparation method is suitable for scale operation.
In addition, by additional thermal treatment, have high-crystallinity and therefore exhibit high brilliance according to the spherical rare earth red phosphor particle of the embodiment of the invention.
The foregoing description and accompanying drawing are not the restriction foregoing invention, and it is evident that for the those of ordinary skill that is relevant to the field of the invention, and it all is possible not departing from that various in the technical essential scope of the present invention substitute, modify and change.
Claims (3)
1. one kind transforms the method for preparing the spherical rare-earth phosphor particles by droplet-particle, comprising:
In rare earth oxide, add acid and have the starting raw material preparation process of starting raw material of the rare earth ion concentration of 0.005M～2.0M scope with preparation respectively;
The urea mixing step that in starting raw material, adds urea;
Mixture forms step through supersonic spraying with the drop that forms drop;
The droplet of evaporation, drying and pyrolysis drop-particle step of converting; With
Washing is also dry through pervaporation, drying and pyrolytic particulate powder formation step,
Wherein, the urea that uses in the urea mixing step is mixed with powder type, and the starting raw material of relative 100 weight parts, with the amount adding of 1～10 weight part,
Wherein, in droplet-particle step of converting, evaporation is carried out at 100～300 ℃, dry carry out at 400～600 ℃, and pyrolysis carries out at 700～1000 ℃, and order is not finished thereby evaporation, drying and pyrolytic process have the ground of overlapping,
Wherein, in droplet-particle step of converting, the drop of mixture is processed with the speed of 1～9L/min.
2. according to the method for claim 1, it randomly comprises after powder forms step, makes the powder that obtains improve step through Overheating Treatment, washing and exsiccant degree of crystallinity.
3. according to the method for claim 2, it is characterized in that, improve the spherical rare-earth phosphor particles for preparing in the step in degree of crystallinity and form powder, mix with Neutral ammonium fluoride, under 900～1600 ℃ of air atmospheres, in calcining furnace, heat-treated 30 minutes～6 hours then with respect to the amount of 5～20 weight parts of the spherical phosphor particles of 100 weight parts.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050079436 | 2005-08-29 | ||
| KR1020050079436A KR100728378B1 (en) | 2005-08-29 | 2005-08-29 | Preparation of Spherical Rare Earth Red Phosphor Particles by Droplet to Particle Conversion |
| KR10-2005-0079436 | 2005-08-29 |
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| CN1923947B true CN1923947B (en) | 2010-08-18 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010038294A (en) * | 1999-10-23 | 2001-05-15 | 윤덕용 | Process for Preparing Aluminate Phosphor Particles by Spray Pyrolysis |
| KR20040042241A (en) * | 2002-11-13 | 2004-05-20 | 한국화학연구원 | Preparation of spherical phosphor having improved photoluminescence and thermal stability |
-
2005
- 2005-08-29 KR KR1020050079436A patent/KR100728378B1/en active IP Right Grant
- 2005-12-26 CN CN2005101376338A patent/CN1923947B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010038294A (en) * | 1999-10-23 | 2001-05-15 | 윤덕용 | Process for Preparing Aluminate Phosphor Particles by Spray Pyrolysis |
| KR20040042241A (en) * | 2002-11-13 | 2004-05-20 | 한국화학연구원 | Preparation of spherical phosphor having improved photoluminescence and thermal stability |
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| KR20070027064A (en) | 2007-03-09 |
| KR100728378B1 (en) | 2007-06-13 |
| CN1923947A (en) | 2007-03-07 |
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