CN102618287A - Method for preparing yellowgreen fluorescent powder for light-emitting diodes (LEDs) - Google Patents
Method for preparing yellowgreen fluorescent powder for light-emitting diodes (LEDs) Download PDFInfo
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- CN102618287A CN102618287A CN2012100750935A CN201210075093A CN102618287A CN 102618287 A CN102618287 A CN 102618287A CN 2012100750935 A CN2012100750935 A CN 2012100750935A CN 201210075093 A CN201210075093 A CN 201210075093A CN 102618287 A CN102618287 A CN 102618287A
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Abstract
The invention relates to a method for preparing yellowgreen fluorescent powder for light-emitting diodes (LEDs), and belongs to the field of preparation of luminescent materials. The method comprises the following steps of: batching, mixing, sintering, crushing, cleaning, drying, sieving and packaging. The method is characterized in that preprocessing step is added before the batching operation, and comprises the following steps of: sieving a matrix material, dehumidifying an activating agent and complexing a fluxing agent to form a composite fluxing agent; according to the mixing step, the dehumidified activating agent and the composite fluxing agent are put into a three-dimensional motion mixer to be mixed, and a premix and the sieved matrix material are introduced into the mixer to be mixed; according to the crushing step, sintered materials are screened by a vibrating screen and an ultrasonic wave classifying screen respectively and are introduced into an air flow crusher to be crushed; according to the cleaning step, powder to be cleaned is cleaned and classified; according to the sieving step, the powder obtained in the drying step is subjected to the particle size classification of finished products; and the powder which is subjected to the particle size classification is packaged to form the yellowgreen fluorescent powder for the LEDs. The method has the advantage that the yellowgreen fluorescent powder has the very ideal primary characteristic and secondary characteristic.
Description
Technical field
The invention belongs to the luminescent material preparing technical field, be specifically related to the preparation method of a kind of LED with the yellow-green fluorescence powder.
Background technology
Because white light LEDs has energy-saving and environmental protection, long service life, WV is low and response speed can satisfy human characteristics such as all requirements to artificial light soon and basically; Thereby be widely used in indoor particularly outdoor (also claim outdoor) illumination; The backlight of screen etc. is shown in outdoor lighting such as Landscape Lighting, stop-light, auto lamp, advertisement and demonstration, be after luminescent lamp and HID lamp the 4th generation light source.
At present, realize that the method for white light LEDs mainly contains following three kinds: the one, on blue chip, apply yellow fluorescent powder (mainly containing YAG:Ce), be mixed into white light by means of blue light and fluorescence; The 2nd, the encapsulation of the chip portfolio of red, green and blue three-color, the luminous white light that directly is mixed into of chip; The 3rd, excite the fluorescent material of three kinds of colors of red, green, blue to be mixed into white light by means of the near-ultraviolet light chip.In these three kinds of methods; Because the circuit relative complex of back two kinds of methods and/or lack suitable fluorescent material or chip; Thereby be difficult to be widely used, and first method is because circuit structure is simple and cost is comparatively cheap, thus in present White-light LED illumination dominate.
In disclosed China and foreign countries patent documentation, be no lack of with the preparing method's of yellow fluorescent powder technical intelligence about LED and be seen in, be not limited to like CN1482208A, CN101126024A (high temperature solid-state method); CN1664063A, CN101249978A (sol-gel method); CN101113333A, CN101012376A (precipitator method); CN1398817A (combustion method); CN1052745C (microwave method); CN1775904A, CN1597841A (vapor phase process); US6614179B1 (high temperature solid-state method).
And then; " a kind of preparation method of Yellow fluorescent powder used by white light LED " that " a kind of white light LEDs is with yellow fluorescent material and be total to the preparation method " that " preparation method of yellow fluorescent powder " that " compound method of phosphor for white light LED " that representative open source literature such as publication No. CN101760196 recommend, " yellow fluorescent powder and preparation method thereof " that CN101914381A provides, CN101948693A introduce, CN101962547A disclose and CN102234511A disclose, or the like.
" compound, comprise its phosphor combination thing and light-emitting device " that " a kind of phosphor material powder and preparation method thereof and white light LED electric light source ", the CN1919854A that " a kind of yellow-green fluorescence powder material and the preparation method " that LED announces with the preparing method's of yellow-green fluorescence powder typical document introduction such as one Chinese patent application publication No. CN102352242A, publication number CN1927996A introduce provides and " a kind of " of CN101824321A announcement based on blue-light excited phosphor for white light LED and preparation method thereof, or the like.
No matter be that LED uses yellow fluorescent powder, or LED uses the yellow-green fluorescence powder, and preparation method each other is basic identical, and the steps in sequence that promptly comprises does; Batching, batch mixing, burn till (sintering), broken (custom be called pulverize or ball milling), clean, dry and sieve, obtain LED with yellow or yellow-green fluorescence powder.
Such as industry knowledge, the up-conversion of ruddiness-visible light can be divided three classes according to the composition of matrix; One is halogen contained compound; Two is sulfide and oxide compound; Three are activator (being mainly REE).Choice of base depends on phonon energy; Generally; The phonon energy of matrix is big more; The relaxation that the rare earth ion generation is radiationless (also claiming to move to jump) is just strong more, and last turnover ratio is just low more, and the material of therefore when preparing luminescent material, selecting to have lower phonon cut-off energy just can obtain higher up-conversion luminescence efficient (specifically can roll up the 2nd phase P123-126 referring to " Chinese rare-earth journal " the 21st).
The substrate material of fluorescent material mainly contains with Al
2O
3Aluminate fluorescent powder for representative; With B
2O
3Borate fluorescent powder for representative; And with SiO
2Be the silicate fluorescent powder of representative, however the most frequently used be with Al
2O
3Aluminate fluorescent powder for representative.
There is the logical fraud of following two aspects in LED in the prior art with the preparation method of yellow-green fluorescence powder: one of which, because substrate material (Al to obtaining by commercially available channel
2O
3, Lu
2O
3And Ga
2O
3), activator (CeO
2) and fusing assistant H
3BO
3Lack the pre-process measure, thereby be difficult to select that to prepare required fluorescent material, luminous intensity and luminescent properties with approaching relatively particle diameter specification poor.Because it is that LED buys from commercially available channel with the production firm of yellow-green fluorescence powder and by the Al as one of main matrix material shown in Figure 1
2O
3Only roughly satisfy D
50Require (to annotate: D
50Also be meso-position radius or median particle diameter, and D
50Mean particle size in order to the expression powder), more particularly, because Al
2O
3Existing particle diameter is the aluminum oxide about 5.2 μ m in the substrate material; It is the aluminum oxide of 1-3 μ m that particle diameter is arranged again; Also having particle diameter is the aluminum oxide of 9-15 μ m; Therefore the particle size distribution range broad prepares required fluorescent material thereby be difficult to select with approaching relatively particle diameter specification, finally causes in high temperature solid state reaction, occurring the big phenomenon of globule size difference of lattice.Again because in view of rare-earth activated agent material such as CeO
2Add-on in whole prescription is with respect to substrate material (Al
2O
3, Lu
2O
3And Ga
2O
3) less; Add the rare earth material moisture absorption of making moist easily; Often water ratio is ignored, promptly do not dehumidified, foot phenomenon occurs so have not at the high temperature solid state reaction process middle-weight rare earths quantity of material of processing fluorescent material; Cause reacting the product lattice defectiveness of generation, thereby the luminous intensity of fluorescent material is produced certain influence.Also because since fusing assistant in ion diffusion and form in the whole process of luminous host and play an important role with perfect lattice; Not only the crystal grain distribution of fluorescent material, luminous efficiency etc. are exerted an influence; And the hardness of agglomerate exerted an influence; If hardness is excessive, then in subsequent disposal, can destroy crystal morphology, influence the generation performance of fluorescent material; Its two because the substrate material (Al that in the batch mixing step, will take by weighing by weight usually
2O
3, Lu
2O
3And Ga
2O
3) activator (CeO
2) and fusing assistant (H
3BO
3) put into rotary container and mix or put into stir shaft type stirred vessel and mix, and this each stirred vessel can only be made circumferential motion, therefore can only obtain degree relatively uniformly by prolonging mixing time (being generally about 40 hours).Yet, owing to mix for a long time, again because various raw materials are the dry type powder; Therefore under moving for a long time, mutual friction of powder phase and heating increase viscosity; And in friction process, produce static, cause agglomeration, the compound that this mixing method obtains is by shown in Figure 2; This Fig. 2 is ESEM (SEM) figure, as can be seen from Figure 2, even if through reaching the mixing about 40 hours; But mixed effect still is unsatisfactory; And the mixed effect shortcoming account in can causing filling a prescription the less active material of share and flux material can not be dispersed in uniformly substrate material around, it is bigger to show as around the substrate material flux material more grain growing that distributes in the high temperature solid state reaction process, on the contrary side is little; The active material more lattice growth that distributes is complete around the substrate material, otherwise the side lattice imperfection is serious.Because these drawbacks; The yellow fluorescence powder even particle size distribution property by shown in Figure 3 that obtains comparatively is short of; The lattice pattern is inconsistent, finally causes all relatively poor (primary characteristic: absorption spectrum, excitation spectrum, emmission spectrum, quantum yield and luminous efficiency etc. of the primary characteristic of fluorescent material and quadratic behavior; Quadratic behavior: dispersiveness, stability and light decay characteristic); Its three, by shown in Figure 4, owing to usually ball milling is adopted in the pulverizing of the powder (custom claims to burn till powder) that burns till; Therefore in powder and ball-milling medium such as agate ball, glass sphere and/or corundum ball friction process, though macrobead is able to fragmentation, the powder of small particle size is also ground carefullyyer thereupon; So according to the known reason of industry; When diameter of particle is following less than 1 μ m, almost no longer possess luminous effect, thereby cause powder granularity wide, the inefficacy incandescnet particle is on the high side.If adopt airflow crash purely; Although the degree that wrecks of lattice significantly is lower than ball milling so, since before putting into comminution by gas stream for want of to the dismission process of agglomerating particles; Thereby; Powder self bump differs greatly, and causes discontinuity, so can produce the shortcoming of ball milling equally; They are four years old; By shown in Figure 5, introduce the container that has whisking appliance and stir owing in cleaning step, will pass through broken powder (dry powder) usually, anhydrate after waiting to leave standstill clarification; And repeatedly for several times; Thereby in this process, objectively be difficult to ultrafine powder and macrobead footpath powder are removed, thereby cause size distribution wide, because ultrafine powder (particle diameter≤1 μ m) does not have luminous efficacy; Its five owing to will clean and the powder after oven dry only sieves through the 100-250 mesh sieve, packing at once, thereby cause and have fine grain size and the big particle diameter powder phenomenon that coexists in the yellow-green fluorescence powder specifically can be referring to Fig. 6.
In view of above-mentioned prior art, be necessary to improve, for this reason, the applicant has done positive and useful making repeated attempts, and the technical scheme that will introduce below produces under this background.
Summary of the invention
Task of the present invention is to provide a kind of and helps to select the substrate material of concentrating relatively with size distribution pointedly and use and satisfy the fluorescent material requirement that preparation has good primary characteristic and quadratic behavior; Help controlling the activator water ratio and use and ensure that fluorescent material has ideal lattice pattern and uses and improve luminous intensity and thermostability; Be of value to the homogeneity that the crystal grain that improves fluorescent material distributes and use and improve luminous efficiency and be convenient to promote substrate material with having; Activator and fusing assistant three's mixed effect and use and ensure that the powder granularity process is evenly distributed; Lattice complete shape and appearance and have and be good at abandoning the inefficacy incandescnet particle and be able to control the preparation method of the LED of particle distribution scope with the yellow-green fluorescence powder.
Task of the present invention is accomplished like this; A kind of LED is with the preparation method of yellow-green fluorescence powder; The steps in sequence that this method comprises is batching, batch mixing, burn till, broken, the packing of cleaning, dry and sieve, and wherein, described batching is for to take by weighing substrate material, take by weighing activator and to take by weighing fusing assistant by mass percent; Be characterised in that: before described batching step, have additional the pre-process step; This pre-process step comprises the screening of said substrate material, is re-dubbed compound fusing assistant to said activator dehumidifying with to said fusing assistant, and described batch mixing is that the activator that will pass through dehumidifying earlier drops in the three-dimensional motion mixer with compound fusing assistant and mixes, and the control mixing time and the speed of mainshaft of controlling three-dimensional motion mixer; Obtain Preblend; Again Preblend is introduced in the three-dimensional motion mixing tank with the substrate material of screening jointly and mixed, and the speed of mainshaft of the mixing time of control three-dimensional motion mixing tank and control three-dimensional motion mixing tank, material to be burnt till obtained; Described fragmentation be with by said burn till that step obtains burn till powder earlier by the vibratory screening apparatus screening, again by the screening of UW sizing screen, then introduce micronizer mill and pulverize, obtain powder to be cleaned, and the intake pressure of control micronizer mill with go out atmospheric pressure; Described cleaning is described powder to be cleaned to be introduced to clean in the classification of sedimentation device clean and classification, obtains fractionated powder to be dried; Described sieving is that the powder that is obtained by baking step is carried out the finished product size classification through the air classification sieve, behind packaging step, obtains LED and uses the yellow-green fluorescence powder.
In a concrete embodiment of the present invention, described substrate material screening is to adopt the airflow classification sieve to sieve into the Three Estate that particle diameter is 1-4.4 μ m, 4.5-6.5 μ m and 6.6-10 substrate material; Described dehumidifying is activator to be inserted in the baking oven cure to activator, and controls stoving temperature and cure the time, and the water ratio of control activator.
In another concrete embodiment of the present invention, the mixing time of described control three-dimensional motion mixer is that mixing time is controlled to be 3-4h, and the speed of mainshaft of described control three-dimensional motion mixer is that the speed of mainshaft is controlled to be 8-12r/min; The mixing time of described control three-dimensional motion mixing tank is controlled to be 10-20h, and the speed of mainshaft of described control three-dimensional motion mixing tank is that the speed of mainshaft is controlled to be 12-18r/min.
In another concrete embodiment of the present invention, described substrate material is Al
2O
3, Lu
2O
3And Ga
2O
3Mixture; Described activator is CeO
2Described compound fusing assistant is H
3BO
3, BaF
2, AlF
2And SrF
2Compsn.
In another concrete embodiment of the present invention; Described control stoving temperature is that temperature is controlled to be 100-120 ℃; The described control time of curing is that the time is controlled to be 60-240min, and the water ratio of described control activator is that water ratio is controlled to be 0.05-0.5%.
Also has among the concrete embodiment described Al of the present invention
2O
3Mass percent be 13-25%, described Lu
2O
3Mass percent be 60-72.5%, described Ga
2O
3Mass percent be 2-14%, described CeO
2Mass percent be 0.3-5.8%; Described by H
3BO
3, BaF
2, AlF
2And SrF
2The mass percent of the compsn that constitutes is 0.18-7.18%, wherein: described H
3BO
3Mass percent be 7-25%, described BaF
2Mass percent be 25-48%, described AlF
2Mass percent be 25-41%, described SrF
2Mass percent be 4-25%.
more of the present invention and among concrete embodiment, the order number of described vibratory screening apparatus is the 200-250 order; The order number of described UW sizing screen is the 300-500 order, and it is the D that gets by UW sizing screen sieve that described micronizer mill is pulverized
50Particle diameter is that the powder of 10-20 μ m is crushed to D
50Particle diameter is the powder of 7-8 μ m, and the intake pressure of described control micronizer mill is that intake pressure is controlled to be 0.8-1.2MPa with going out atmospheric pressure, and the pressure-controlling of will giving vent to anger is 0.4-0.8MPa.
In of the present invention and then concrete embodiment, described cleaning classification of sedimentation device comprises that one has the stirred vessel of whisking appliance; One first extracts mechanism, one second extracts mechanism and one the 3rd extraction mechanism, and first extracts mechanism comprises first timing control valve, first extraction pump, first bucket and first pipeline, and first timing control valve and first extraction pump are connected to the middle part of first pipeline in turn; One end of first pipeline is connected with the top of the short transverse of stirred vessel; And the other end of first pipeline is stretched in first bucket, and wherein, first timing control valve is between the stirred vessel and first extraction pump; Second extracts mechanism comprises second timing control valve, second extraction pump, second bucket and second pipeline; Second timing control valve and second extraction pump are connected to the middle part of second pipeline in turn, and an end of second pipeline is connected with the middle part of the short transverse of stirred vessel, and the other end of second pipeline is stretched in second bucket; Wherein, Second timing control valve is between the stirred vessel and second extraction pump, and the 3rd extracts mechanism comprises the 3rd timing control valve, the 3rd extraction pump, the 3rd bucket and the 3rd pipeline, and second timing control valve and second extraction pump are connected to the middle part of the 3rd pipeline in turn; One end of the 3rd pipeline is connected with the bottom of the short transverse of stirred vessel; And the other end of the 3rd pipeline is stretched in the 3rd bucket, and wherein, the 3rd timing control valve is between stirred vessel and the 3rd extraction pump.
Of the present invention again more and among concrete embodiment, described to carry out the finished product size classification through the air classification sieve be that the powder branch that said baking step obtains is sifted out particle size distribution range is D
10=3-5 μ m, D
50=7-8 μ m and D
90The finished product powder of=10-12 μ m.
Technical scheme provided by the invention is owing to sieved before batch mixing host material; Thereby the host material that can select the particle diameter distribution to concentrate is relatively put into follow-up batch mixing step and activator and flux mixed together; Powder granularity to satisfy preparation is evenly distributed; The lattice complete shape and appearance, final so that fluorescent material has excellent primary characteristic and quadratic behavior; Because activator is dehumidified; Thereby effectively controlled the activator moisture content and be able to ensure that fluorescent material has desirable lattice pattern and improves luminous efficiency and heat endurance (fading rate of light), make the fluorescent material brightness of making improve 5-10%, the fading rate of light has reduced 10-20%; Because flux is re-dubbed composite fluxing agent; Thereby can reduce firing temperature in the step in follow-up burning till; Firing temperature is reduced to 1400-1500 ℃ by the 1550-1650 in the prior art ℃; Not only can prolong the service life of firing furnace; And embody energy-conservationly, and can effectively control the hardness of firing powder in addition, improved in the powder last handling process owing to the excessive lattice damage that causes of the hardness of powder; Promote the crystal grain distributing homogeneity of fluorescent material, improved the luminous efficiency of fluorescent material; Owing to activator and flux are mixed the premix that obtains mutually mix with host material again; And adopt three-dimensional motion mixing method batch mixing; Thereby can obtain desirable mixed effect; Make and make powder granularity and be evenly distributed; The lattice complete shape and appearance; And, ensure fully that therefore the yellow-green fluorescence powder that obtains has very good primary characteristic and quadratic behavior owing to abandoned the inefficacy incandescnet particle and controlled the distribution of particles scope.
Description of drawings
The substrate material Al that Fig. 1 buys for commercially available channel
2O
3Sem photograph.
Fig. 2 is with the sem photograph of substrate material, activator and the disposable mixed compound of fusing assistant three in the prior art.
Fig. 3 is the sem photograph of the yellow-green fluorescence powder in the prior art.
The particle distribution figure of the window of tube light powder that Fig. 4 obtains after for ball milling in the prior art.
Fig. 5 is the phosphor particles distribution plan after cleaning in the prior art.
Fig. 6 is the sem photograph after the powder after the oven dry being sieved through the 100-250 mesh sieve in the prior art.
Fig. 7 is that the inventive method is to substrate material Al
2O
3Adopt the sem photograph after the airflow classification sieve sieves.
Fig. 8 earlier mixes the sem photograph of the compound that obtains after by the three-dimensional motion mixing tank substrate material being participated in mixing again with rare-earth activated dose with fusing assistant for the inventive method by means of three-dimensional motion mixer.
The phosphor particles distribution plan of Fig. 9 for obtaining after the inventive method fragmentation.
Figure 10 is the phosphor particles distribution plan of the inventive method after cleaning.
Figure 11 is the used cleaning classification of sedimentation device synoptic diagram of the inventive method.
Figure 12 carries out the sem photograph of the yellow-green colour powder that the finished product size classification obtains for the powder of the inventive method after to oven dry.
Embodiment
Embodiment 1:
Ask for an interview Fig. 7 to Figure 12.
LED may further comprise the steps with the preparation method of yellow-green fluorescence powder: batching, batch mixing, burn till, broken, clean, dry and sieve; Wherein: described batching is for to take by weighing substrate material, take by weighing activator and to take by weighing fusing assistant by mass percent, and substrate material is Al
2O
3, Lu
2O
3And Ga
2O
3Mixture, Al wherein
2O
3The mass percent of (through screening) is 25%, Lu
2O
3Mass percent be 60%, Ga
2O
3Mass percent be 2.2%, activator is CeO
2, this CeO
2Mass percent be 5.8%, fusing assistant is H
3BO
3, BaF
2, AlF
2And SrF
2Compsn, promptly compound fusing assistant, the mass percent of this compound fusing assistant are 7%, wherein: H in the compound fusing assistant
3BO
3Mass percent be 25%, BaF
2Mass percent be 46%, AlF
2Mass percent be 25%, SrF
2Mass percent be 4%.As the technical essential of technical scheme provided by the invention, before getting into batching to the Al of aforementioned substrate material
2O
3, to activator CeO
2And to fusing assistant promptly by H
3BO
3, BaF
2And AlF
2And SrF
2The compound fusing assistant that constitutes carries out pre-process, and that is to say before batching step increases the pre-process step, specifically: with Al
2O
3Adopt the airflow classification screening to sieve into the Three Estate that particle diameter is 1-4.4 μ m, 4.5-6.5 μ m and 6.6-10 μ m (present embodiment is selected 4.5-6.5 μ m grade for use), from this Three Estate, choose the Al of one of them grade during for the yellow fluorescent powder of producing demands of different
2O
3, the Al after the screening of airflow classification sieve
2O
3The particle diameter degree of uniformity can illustrate by Fig. 7; With activator is CeO
2Send into oven-baked and promptly dehumidify, oven temperature is 120 ℃, and the time of curing is 200min, and going out baking oven, to obtain water ratio be 0.2% activator; Earlier with fusing assistant promptly by H
3BO
3, BaF
2And AlF
2And SrF
2The compsn that mixes is compound fusing assistant and activator CeO
2Together drop in the three-dimensional motion mixer and mix; Three-dimensional motion mixer is preferred but not to select the model of being produced by the long-range mechanical ltd in Chinese Guangdong province Shenzhen for use be the multidirectional motion mixing tank of SYH-200 type with being limited to; Mixing time is 3h; The speed of mainshaft of this multidirectional motion mixing tank is 10r/min, obtains Preblend, the substrate material Al that is 4.5-6.5 μ m with Preblend and aforesaid screening particle diameter grade again
2O
3, and equally as the Lu of substrate material
2O
3And Ga
2O
3Drop in the three-dimensional motion mixing tank and mix 20h; The speed of mainshaft of three-dimensional motion mixing tank is controlled to be 15r/min; In the present embodiment; Described three-dimensional motion mixing tank is preferred but not to select the model of being produced by the long-range mechanical ltd in Chinese Guangdong province Shenzhen equally for use be the multidirectional motion mixing tank of SYH-800 type with being limited to, and the particle diameter that obtains waiting to burn till material is by shown in Figure 8
The multidirectional motion mixing tank of SYH-200 type of mentioning in the present embodiment and SYH-800 type by main shaft passive and universal joint supporting mixing tank to do three-dimensional motion in X, Y and Z-direction; Mixing tank is also made revolution motion except spinning motion; Make the material in the mixing tank make diffusional flow and shearing motion every now and then; Strengthened to best the mixed effect of material,, overcome the influence that produces cf-when adopting rotary container or stir shaft type stirred vessel to mix in the prior art because of the three-dimensional motion of mixing tank; Reduce the material gravity segregation, thereby guaranteed mixed effect.Embodied applicant's alleged technique effect in the technique effect hurdle all sidedly.
Will to introduce the order number earlier be that 200 purpose vibratory screening apparatuss are the moto-vibro screen screening by the powder that burns till that burns till that step obtains; Screen by UW sizing screen (also claiming the ultrasonic vibration sizing screen) again; The order number of UW sizing screen is 500 orders; Make the particle diameter of powder be controlled to be 10-20 μ m, then introduce micronizer mill and pulverize, micronizer mill preferred but not uses the model by the production of the mechanical ltd of the pioneer of Changshu City, Jiangsu Province, China to be GTM-400 type kibbler with being limited to; This micronizer mill is ceramic-lined flat kibbler; Make the D50 particle diameter of powder be controlled to be 7-8 μ m, the inlet, outlet pressure of micronizer mill is respectively 0.8MPa and 0.4MPa, and obtaining powder to be cleaned after being pulverized by micronizer mill is that phosphor particles is illustrated by Fig. 9.
Utilization is cleaned the powder aforementioned to be cleaned that obtains after being pulverized by micronizer mill by the cleaning classification of sedimentation device of Figure 11, and the applicant at first describes the structure of cleaning the classification of sedimentation device, comprises that one has the stirred vessel 1 of whisking appliance 11; One first extracts mechanism 2, one second extracts mechanism 3 and one the 3rd extraction mechanism 4; First extracts mechanism 2 comprises first timing control valve 21, first extraction pump 22, first bucket 23 and first pipeline 24; First timing control valve 21 and first extraction pump 22 are connected to the middle part of first pipeline 24 in turn, and an end of first pipeline 24 is connected with the top of the short transverse of stirred vessel 1, and the other end of first pipeline 24 is stretched in first bucket 23; Wherein, First timing control valve 21 is between the stirred vessel 1 and first extraction pump 22, and second extracts mechanism 3 comprises that second timing control valve 31, second extraction pump 32, second bucket 33 and second pipeline, 34, the second timing control valves 31 and second extraction pump 32 are connected to the middle part of second pipeline 34 in turn; One end of second pipeline 34 is connected with the middle part of the short transverse of stirred vessel 1; And the other end of second pipeline 34 is stretched in second bucket 33, and wherein, second timing control valve 31 is between the stirred vessel 1 and second extraction pump 32; The 3rd extracts mechanism 4 comprises the 3rd timing control valve 41, the 3rd extraction pump 42, the 3rd bucket 43 and the 3rd pipeline 44; Second timing control valve 41 and second extraction pump 42 are connected to the middle part of the 3rd pipeline 44 in turn, and an end of the 3rd pipeline 44 is connected with the bottom of the short transverse of stirred vessel 1, and the other end of the 3rd pipeline 44 is stretched in the 3rd bucket 43; Wherein, the 3rd timing control valve 41 is between stirred vessel 1 and the 3rd extraction pump 32.The applicant describes method or the title process that the agitation powder is implemented cleaning: powder to be cleaned is introduced in the stirred vessel 1; And introduce deionized water (mending ratio) turn on agitator 11 into 4 liters of deionized waters in kilogram fluorescent material per kilogram; The rotating speed of whisking appliance is 15-20r/min, treat that whisking appliance stirs 25-35min after, according to sequencing open first extract mechanism 2 first timing control valve 21; 22 work of first extraction pump; The powder slurry solution on the top in the stirred vessel 1 is introduced in first bucket 23 through first pipeline 24, then opened second timing control valve, 31, the second extraction pumps, 32 work of the second extraction mechanism 3; The powder slurry solution that is positioned at the middle part in the stirred vessel 1 is introduced second bucket 33 through second pipeline 34; Then open the 3rd timing control valve 41, the three extraction pumps 42 work of the 3rd extraction mechanism 4, with powder slurry solution warp the 3rd pipeline 44 introducings the 3rd bucket 43 that is positioned at the bottom in the stirred vessel 1.Then, the slurry of the powder in first, second, third bucket 23,33,43 is introduced whizzer respectively dry, waiting of obtaining dried phosphor particles distribution scenario after the cleaning that powder promptly obtains by shown in Figure 10.This step is the principle that has different settling velocity according to different diameter of particle; Extract slurries that mechanism 2 extracts by first and promptly be arranged in the slurries on stirred vessel 1 top because powder granularity is ultra-fine and be mingled with the foreign material that cleaning process produces; Therefore usually that it is discarded; And by second extract that mechanism 3 extracts be normal powder (finished powder), and lower floor promptly to extract the diameter of particle that mechanism 4 extracts by the 3rd bigger, need to handle the back again and use.In view of the above, phosphor particles distribution scenario shown in Figure 10 is to extracting mechanism's 3 powders that extract and behind centrifuge dripping by second.
The fractionated that after above-mentioned cleaning, obtains waits to dry powder dries according to the same process in the prior art; And the back packing of sieving; Yet as technical essential of the present invention: the powder that baking step is obtained carries out the finished product size classification through the air classification sieve, obtains D
10=3-5 μ m, D
50=7-8 μ m and D
90=10-12 μ m; Obtain the high-quality powder of size distribution high concentration; It is even to that is to say that the yellow-green colour powder to be packaged that after the air classification sieve carries out the finished product size classification, obtains has size of particles, and no agglomeration and lattice perfection between the particle are specifically illustrated by Figure 12.
The resulting LED of present embodiment has the strong point of narrow diameter distribution with the yellow-green fluorescence powder; Compare with the yellow-green fluorescence powder of prior art; Through analytical test: brightness improves 3-5%, the particle diameter uniformity coefficient improves more than 30%; Lattice imperfection reduces about 30%, thereby can reduce the light decay and the look drift of fluorescent material, improves thermostability.
Embodiment 2:
Only will pass through the Al of screening
2O
3Mass percent change 13% into, with Lu
2O
3Mass percent change 72.5% into, with Ga
2O
3Mass percent change 14% into, with CeO
2Mass percent be 0.3%, will be by H
3BO
3, BaF
2And AlF
2The compsn that constitutes is that the mass percent of compound fusing assistant changes 0.2% into, wherein: H
3BO
3Mass percent change 8% into, BaF
2Mass percent change 40% into, AlF
2Mass percent change 41% into, SrF
2Mass percent change 11% into; Al
2O
3Get the particle diameter grade of 6.6-10 μ m; To CeO
2Stoving temperature and time change 100 ℃ and 240min, CeO respectively into
2Water ratio be 0.07%; Change the mixing time of compound fusing assistant and activator into 4h, the speed of mainshaft of three-dimensional motion mixer is that the speed of mainshaft of multidirectional motion mixing tank changes 8r/min into, is that the substrate material of 6.6-10 μ m is Al with Preblend and particle diameter
2O
3And same Lu as substrate material
2O
3And Ca
2O
3Mixing time change 10h into, the speed of mainshaft of three-dimensional motion mixing tank changes 18r/min into; Change the order number of vibratory screening apparatus into 250 orders, change the order number of UW sizing screen into 300 orders, change the inlet, outlet pressure of micronizer mill into 1.2MPa and 0.8MPa respectively, all the other are all with the description to embodiment 1.
Embodiment 3:
Only will pass through the Al of screening
2O
3Mass percent change 20% into, with Lu
2O
3Mass percent change 65% into, with Ga
2O
3Mass percent change 8% into, with CeO
2Mass percent be 2.5%, will be by H
3BO
3, BaF
2And AlF
2The compsn that constitutes is that the mass percent of compound fusing assistant changes 4.5% into, wherein: H
3BO
3Mass percent change 10% into, BaF
2Mass percent change 35% into, AlF
2Mass percent change 30% into, SrF
2Mass percent change 25% into; Al
2O
3Get the particle diameter grade of 1-4.4 μ m; To CeO
2Stoving temperature and time change 110 ℃ and 70min, CeO respectively into
2Water ratio be 0.5%; Change the mixing time of compound fusing assistant and activator into 3.5h, the speed of mainshaft of three-dimensional motion mixer is that the speed of mainshaft of multidirectional motion mixing tank changes 12r/min into, is that the substrate material of 1-4.4 μ m is Al with Preblend and particle diameter
2O
3And same Lu as substrate material
2O
3And Ca
2O
3Mixing time change 15h into, the speed of mainshaft of three-dimensional motion mixing tank changes 13r/min into; Change the order number of vibratory screening apparatus into 220 orders, change the order number of UW sizing screen into 400 orders, change the inlet, outlet pressure of micronizer mill into 1MPa and 0.6MPa respectively, all the other are all with the description to embodiment 1.
Claims (9)
1.
a kind of LED is with the preparation method of yellow-green fluorescence powder; The steps in sequence that this method comprises is batching, batch mixing, burn till, broken, the packing of cleaning, dry and sieve; Wherein, Described batching is characterized in that for to take by weighing substrate material, take by weighing activator and to take by weighing fusing assistant by mass percent: before described batching step, have additional the pre-process step, this pre-process step comprises said substrate material screening, is re-dubbed compound fusing assistant to said activator dehumidifying with to said fusing assistant; Described batch mixing is that the activator that will pass through dehumidifying earlier drops in the three-dimensional motion mixer with compound fusing assistant and mixes; And the speed of mainshaft of control mixing time and control three-dimensional motion mixer obtains Preblend, Preblend is introduced in the three-dimensional motion mixing tank with the substrate material of screening jointly mixed again; And the mixing time of control three-dimensional motion mixing tank and the speed of mainshaft of control three-dimensional motion mixing tank obtain material to be burnt till; Described fragmentation be with by said burn till that step obtains burn till powder earlier by the vibratory screening apparatus screening, again by the screening of UW sizing screen, then introduce micronizer mill and pulverize, obtain powder to be cleaned, and the intake pressure of control micronizer mill with go out atmospheric pressure; Described cleaning is described powder to be cleaned to be introduced to clean in the classification of sedimentation device clean and classification, obtains fractionated powder to be dried; Described sieving is that the powder that is obtained by baking step is carried out the finished product size classification through the air classification sieve, behind packaging step, obtains LED and uses the yellow-green fluorescence powder.
2.
LED according to claim 1 is characterized in that with the preparation method of yellow-green fluorescence powder described substrate material screening is to adopt the airflow classification sieve to sieve into the Three Estate that particle diameter is 1-4.4 μ m, 4.5-6.5 μ m and 6.6-10 substrate material; Described dehumidifying is activator to be inserted in the baking oven cure to activator, and controls stoving temperature and cure the time, and the water ratio of control activator.
3.
LED according to claim 1 is with the preparation method of yellow-green fluorescence powder; The mixing time that it is characterized in that described control three-dimensional motion mixer is that mixing time is controlled to be 3-4h, and the speed of mainshaft of described control three-dimensional motion mixer is that the speed of mainshaft is controlled to be 8-12r/min; The mixing time of described control three-dimensional motion mixing tank is controlled to be 10-20h, and the speed of mainshaft of described control three-dimensional motion mixing tank is that the speed of mainshaft is controlled to be 12-18r/min.
4.
LED according to claim 1 is characterized in that with the preparation method of yellow-green fluorescence powder described substrate material is Al 2 O 3 , Lu 2 O 3 And Ga 2 O 3 Mixture; Described activator is CeO 2 Described compound fusing assistant is H 3 BO 3 , BaF 2 , AlF 2 And SrF 2 Compsn.
5.
LED according to claim 2 is with the preparation method of yellow-green fluorescence powder; It is characterized in that described control stoving temperature is that temperature is controlled to be 100-120 ℃; The described control time of curing is that the time is controlled to be 60-240min, and the water ratio of described control activator is that water ratio is controlled to be 0.05-0.5%.
6.
LED according to claim 4 is characterized in that described Al with the preparation method of yellow-green fluorescence powder 2 O 3 Mass percent be 13-25%, described Lu 2 O 3 Mass percent be 60-72.5%, described Ga 2 O 3 Mass percent be 2-14%, described CeO 2 Mass percent be 0.3-5.8%; Described by H 3 BO 3 , BaF 2 , AlF 2 And SrF 2 The mass percent of the compsn that constitutes is 0.18-7.18%, wherein: described H 3 BO 3 Mass percent be 7-25%, described BaF 2 Mass percent be 25-48%, described AlF 2 Mass percent be 25-41%, described SrF 2 Mass percent be 4-25%.
7.
LED according to claim 1 is with the preparation method of yellow-green fluorescence powder, and the order number that it is characterized in that described vibratory screening apparatus is the 200-250 order; The order number of described UW sizing screen is the 300-500 order, and it is the D that gets by UW sizing screen sieve that described micronizer mill is pulverized 50 Particle diameter is that the powder of 10-20 μ m is crushed to D 50 Particle diameter is the powder of 7-8 μ m, and the intake pressure of described control micronizer mill is that intake pressure is controlled to be 0.8-1.2MPa with going out atmospheric pressure, and the pressure-controlling of will giving vent to anger is 0.4-0.8MPa.
8.
LED according to claim 1 is characterized in that with the preparation method of yellow-green fluorescence powder described cleaning classification of sedimentation device comprises that one has the stirred vessel (1) of whisking appliance (11); One first extracts mechanism (2), one second extracts mechanism (3) and one the 3rd extraction mechanism (4); First extracts mechanism (2) comprises first timing control valve (21), first extraction pump (22), first bucket (23) and first pipeline (24); First timing control valve (21) and first extraction pump (22) are connected to the middle part of first pipeline (24) in turn; One end of first pipeline (24) is connected with the top of the short transverse of stirred vessel (1); And the other end of first pipeline (24) is stretched in first bucket (23), and wherein, first timing control valve (21) is positioned between stirred vessel (1) and first extraction pump (22); Second extracts mechanism (3) comprises second timing control valve (31), second extraction pump (32), second bucket (33) and second pipeline (34); Second timing control valve (31) and second extraction pump (32) are connected to the middle part of second pipeline (34) in turn, and an end of second pipeline (34) is connected with the middle part of the short transverse of stirred vessel (1), and the other end of second pipeline (34) is stretched in second bucket (33); Wherein, Second timing control valve (31) is positioned between stirred vessel (1) and second extraction pump (32), and the 3rd extracts mechanism (4) comprises the 3rd timing control valve (41), the 3rd extraction pump (42), the 3rd bucket (43) and the 3rd pipeline (44), and second timing control valve (41) and second extraction pump (42) are connected to the middle part of the 3rd pipeline (44) in turn; One end of the 3rd pipeline (44) is connected with the bottom of the short transverse of stirred vessel (1); And the other end of the 3rd pipeline (44) is stretched in the 3rd bucket (43), and wherein, the 3rd timing control valve (41) is positioned between stirred vessel (1) and the 3rd extraction pump (32).
9.
LED according to claim 1 is with the preparation method of yellow-green fluorescence powder, it is characterized in that described to carry out the finished product size classification through the air classification sieve be that the powder branch that said baking step obtains is sifted out particle size distribution range is D 10 =3-5 μ m, D 50 =7-8 μ m and D 90 The finished product powder of=10-12 μ m
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103122484A (en) * | 2013-01-10 | 2013-05-29 | 华北电力大学 | Method for regulating and controlling luminescent characteristic of CsI(Na) crystal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060145124A1 (en) * | 2004-12-31 | 2006-07-06 | Industrial Technology Research Institute | Method for preparing YAG fluorescent powder |
| CN1818016A (en) * | 2005-11-28 | 2006-08-16 | 常熟市江南荧光材料有限公司 | Synthesis of YAG luminescent material for white LED |
| CN101186817A (en) * | 2007-11-28 | 2008-05-28 | 太原理工大学 | Method for preparing yellow light type fluorescent powder |
| DE102008032299A1 (en) * | 2008-07-09 | 2010-01-14 | Osram Gesellschaft mit beschränkter Haftung | Process for the preparation of a garnet phosphor |
-
2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060145124A1 (en) * | 2004-12-31 | 2006-07-06 | Industrial Technology Research Institute | Method for preparing YAG fluorescent powder |
| CN1818016A (en) * | 2005-11-28 | 2006-08-16 | 常熟市江南荧光材料有限公司 | Synthesis of YAG luminescent material for white LED |
| CN101186817A (en) * | 2007-11-28 | 2008-05-28 | 太原理工大学 | Method for preparing yellow light type fluorescent powder |
| DE102008032299A1 (en) * | 2008-07-09 | 2010-01-14 | Osram Gesellschaft mit beschränkter Haftung | Process for the preparation of a garnet phosphor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122484A (en) * | 2013-01-10 | 2013-05-29 | 华北电力大学 | Method for regulating and controlling luminescent characteristic of CsI(Na) crystal |
| CN103122484B (en) * | 2013-01-10 | 2015-04-15 | 华北电力大学 | Method for regulating and controlling luminescent characteristic of CsI(Na) crystal |
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