CN101113333A - Method for preparing cerium-activated yttrium aluminium garnet fluorescent powder - Google Patents
Method for preparing cerium-activated yttrium aluminium garnet fluorescent powder Download PDFInfo
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- CN101113333A CN101113333A CNA2007100094634A CN200710009463A CN101113333A CN 101113333 A CN101113333 A CN 101113333A CN A2007100094634 A CNA2007100094634 A CN A2007100094634A CN 200710009463 A CN200710009463 A CN 200710009463A CN 101113333 A CN101113333 A CN 101113333A
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Abstract
The invention relates to a preparation method of yttrium aluminum garnet phosphor activated by cerium and a phosphor. The invention provides a generalized preparation method of yttrium aluminum garnet phosphor activated by cerium. A chemical formula is Y3-x-y-zRyAl5-mGamO12: Cex, R'z. The preparation method comprises the steps of: preparation of metal ions solutions, preparation of precipitant solutions, preparation of metal ions precipitants, addition of flux and solid phase reaction, sintering, grinding powders sintered under high temperature, pickling, alkali washing, water washing and drying, then the target product YAG:Ce phosphor, which has high luminous intensity, low agglomeration degree without ball milling, proper powder size and narrow particle size distribution, is obtained; besides, the phosphor has low agglomeration degree after being treaded under high temperature, and the phosphor can be packed and sealed without ball milling and can maximize the excellent optical property.
Description
Technical field
The present invention relates to a kind of fluorescent material, especially relate to a kind of method for preparing the illuminating generalized cerium activated yttrium aluminium garnet of white light emitting diode (LED) (YAG:Ce) fluorescent material with oxalic acid coprecipitation.
Background technology
White light LEDs and combined light source thereof have solidification, volume is little, the life-span is long, antidetonation, not fragile, start that response is fast, current consumption is little and advantage such as nuisanceless, be described as the 4th generation lighting source, be also referred to as the 21 century green light source.Adopting generalized YAG:Ce fluorescent material is the main flow that develops at present.This kind fluorescent material can absorb the blue light of InGaN/GaN chip effectively and send gold-tinted, obtains white light with unabsorbed blue light.Therefore, the progress of YAG:Ce fluorescent material technology of preparing has important effect to the development of white light LEDs.
Preparing the YAG:Ce powder that the reunion degree is little, granularity is fit to, particle shape is good, luminous intensity is high, is one of key of this technology.The method for preparing YAG:Ce fluorescent material at present both at home and abroad mainly contains following several:
(1) high temperature solid-state method: this method is the method that the most generally adopts in the present suitability for industrialized production, and its technology is simple, cost is low, efficient is high, easy batch process; But exist sintering step could carry out smoothly down at high temperature (about 1600 ℃); The powder diameter that makes is bigger than normal and distribute wide; Powder is easily reunited, and often needs to destroy crystal easily through ball milling, causes luminous intensity to descend the degradation shortcoming significantly.Representational document as:
1.Bando K.Development of high-bright and pure-white LED lamps[J] .Light ﹠amp; Vis.Env., 1998, (1) [author is the slip-stick artist of Nichia Chemical Industries, Ltd, and draw certainly: Yang Xiaowei translates. the development [J] of high brightness, pure white LED lamp. and Chinese electric lighting, 2000, (1): 27-29].
2. the patent No. is the Chinese invention patent (patentee is a Nichia Chemical Industries, Ltd, and this patent is mentioned the fluorescent material with the synthetic preparation of solid phase method generalized YAG:Ce, uses barium fluoride and boric acid to be fusing assistant) of ZL 02800161.3.
3. Xu Xu Rong, Su Mianceng. luminescence and luminescent material [M]. Beijing: Chemical Industry Press, 2004.
Publication number be CN1880402A the Chinese invention patent application (application people be Xiamen Topstar Lighting Co., Ltd, the invention people is Wei Lan etc., this patent application discloses with high temperature solid-state method and has prepared YAG:Ce fluorescent material, mention with the oxide compound of yttrium, aluminium, cerium etc. or oxalate etc. and make raw material, narrated the problems such as selection of fusing assistant).
(2) sol-gel method: with the inorganic salt or the metal alkoxide of facile hydrolysis, be raw material,, be converted into gel by colloidal sol through reaction process such as hydrolysis, polycondensations as methyl cellosolve yttrium and isobutanol aluminum solution.Pre-burning under gel drying, the lesser temps, grinding, sintering under comparatively high temps gets YAG fluorescent material at last again.The advantage of this method is that each component concentration is accurately controlled, good uniformity; Can lower temperature (700～1000 ℃) down the YAG powder; Primary particle size is little.But exist the sol-gel method productive rate low; Used organic raw material cost height, and alkoxide is poisonous; Carbon containing ligand under non-oxidized substance atmosphere in the organic ligand is difficult for removing, and residual carbon can influence the body colour and the luminosity of fluorescent material; Shortcomings such as particle agglomeration is also more serious.Relevant document as:
1.Veith?M，Mathur?S，Kareiva?A，et?al.Low?temperature?synthesis?of?nanocrystallineY
3Al
5O
12(YAG)and?Ce-doped?Y
3Al
5O
12?via?different?sol-gel?methods[J].Mater.Chem.1999，12(9)：3069-3079。
2. the patent No. is the Chinese invention patent (this patent adopts gel method to prepare YAG:Ce, and Z fluorescent material, Z are the rare earth element beyond the Ce) of ZL 01120498.2.
(3) spray pyrolysis (spray pyrolysis, SP) method: the SP method is a kind of the metal precursor solution atomization to be sprayed in the High Temperature Furnaces Heating Apparatus, causes the evaporation of solvent and the thermolysis immediately of metal precursor, thus the direct method of synthesis oxide powder.Its remarkable advantage is to make essentially no reunion, spheric nano powder, and the purity height, and controllable granularity easily realizes suitability for industrialized production.But there are hollow easily, the required shortcomings such as apparatus expensive of particle that make.Commonly traditional SP method (so-called " spray pyrolysis single stage method ") is simplified, replaced, to avoid expensive equipment with so-called spraying drying-high-temperature heat treatment " spray pyrolysis two-step approach ".But " spray pyrolysis two-step approach " can only be used to prepare micropowder, as preparation nano powder also handy " spray pyrolysis single stage method ".Representational document as:
1. the work of " spray pyrolysis two-step approachs " such as Japanese Kang and Korea S Park: Kang YC, Lenggoro IW, ParkSB.YAG:Ce particles prepared by ultrasonic spray pyrolysis.J.Mater.Res.Bull, 2000,35 (5): 789-798.
Publication number be CN1962811 the Chinese invention patent application (this application adopt " spray pyrolysis two-step approach " synthesized (Y, Gd)
3Al
5O
12: Ce, promptly mix the YAG:Ce fluorescent material of Gd).
3. the patent No. is the United States Patent (USP) (this patent provides the preparation method about YAG:Ce, is similar to " spray pyrolysis two-step approach ", realizes the preparation method of oxide compound coating) of US7005085.
(4) non-oxalic acid coprecipitation: add suitable precipitation agent (or back titration) in the blended metal salt solution, reaction generates forms precipitation uniformly; After filtration, clean, dry, high temperature sintering, product.Compare with solid reaction process, this method can make the good fluorescent material of chemical uniformity at a lower temperature, can wait the granularity of controlling fluorescent material by concentration, temperature of reaction, the time of conditioned reaction thing.Non-oxalic acid coprecipitation is the method a kind of commonly used of preparation YAG, but used precipitation agent and concrete preparation technology have nothing in common with each other.Relevant document as:
1.Chiang?CC，Tsai?MS，Hsiao?CS，et?al.Synthesis?of?YAG:Ce?phosphor?via?differentaluminum?sources?and?precipitation?processes[J].Alloys?&?Compd.，2006，416(1-2)：265-269。
2.Pan YX, Wu MM, Su Q.Comparative investigation on synthesis and photoluminescence ofYAG:Ce phosphor[J] .Mater.Sci.Eng., B-Solid State Mater.Adv.Technol., 2004,106 (3): 251-256 (this article has been reported with urea and made precipitation agent, has synthesized YAG:Ce fluorescent material with coprecipitation method).
3. Miu Chun swallow, Li Dongping, Liu Lifang waits .YAG:Ce
3+Synthetic and spectrum property research [J]. spectrographic laboratory, 2004,21 (3): 563-565 (this article has been reported hybrid metal solion and bicarbonate of ammonia and ammoniacal liquor mixing solutions are splashed in the same reaction vessel simultaneously, synthesized YAG:Ce fluorescent material).
The patent No. be ZL 200510071958.0 Chinese invention patent (patentee is " Xiamen section is sensible " Wang Jingao, this patent disclosure prepare YAG:Ce fluorescent material with coprecipitation method and sol-gel method, precipitation agent adopts ammoniacal liquor).
(5) oxalic acid coprecipitation: the existing a lot of documents that adopt oxalic acid coprecipitation to prepare broad sense YAG:Ce fluorescent material are clearly mentioned, and this method employing oxalic acid etc. are as precipitation agent, and are similar with common coprecipitation method; Wherein some document is relevant with YAG:Ce fluorescent material for this, but does not mention the relative luminosity of fluorescent material, and work does not also relate to industrialization.What have mentions with the synthetic YAG:Ce fluorescent material of oxalate precipitation method, or does not have details, or is difficult to repetition, or does not belong to coprecipitation method.Relevant document is as follows:
1. publication number is that the U.S. Patent application (open day be on 07 06th, 2006) of US Patent20060145124 is with the synthetic YAG:Ce fluorescent material of co-precipitation; With the volatile salt is precipitation agent, and mentions precipitation agent and can use one or more mixing in oxalic acid, ammoniacal liquor, the volatile salt; But do not provide other details to oxalate precipitation method, the synthetic YAG:Ce fluorescent material of oxalate precipitation method is not had concrete contribution.
2. the patent No. is the United States Patent (USP) of US 6869544.It is the coprecipitation method of precipitation agent that this patent adopts triethylamine, synthesizes YAG:Ce fluorescent material.Mention precipitation agent in the patent and also can use oxalic acid, relevant details but is not provided, also having only triethylamine on the embodiment is precipitation agent, and the synthetic YAG:Ce fluorescent material of oxalate precipitation method is not had concrete contribution yet.
3. the patent No. is the Chinese invention patent (patentee is Beijing Non-Ferrous Metal Research General Academy and Grirem Advance Materials Co., Ltd, and this patent was authorized on May 30th, 2007) of ZL 02130949.3.The groundwork of this patent is the research of the synthetic and composition of high temperature solid-state method, and prescription has covered YAG:Ce, R '
yFluorescent material, yttrium can partly replace with gadolinium etc.; Aluminium can partly replace with gallium etc., and R ' is a praseodymium, one or more of dysprosium etc.This patent has also been reported oxalate precipitation method, and post precipitation adds at least a fusing assistant of fluorochemical, boric acid etc. again through thermal treatment, and pyroprocessing under reducing atmosphere obtains fluorescent material then.But find in experiment that through the present inventor this patent adds the method for oxalic acid separately, be difficult to aluminum precipitation is got off, can cause a large amount of losses of aluminium; This may be the cause of oxalic acid aluminium hydrolysis.In addition, this patent has only compared the emission peak positions and the relative brightness of the powdered sample that oxalic acid coprecipitation and this patentee make with solid phase method, not and the commodity powder relatively, do not mention the possibility of industrialization yet.
4. publication number is that the U.S. Patent application (WO/04/079790) of US Patent 20040173807 has been reported yttrium, aluminium, and the polyionic mixing solutions of cerium adds oxalic acid earlier, makes yttrium and cerium precipitation; After the ageing, add ammoniacal liquor again, aluminum ion is precipitated; Through leaving standstill, remove supernatant liquid, centrifugal, washing with acetone; Heat-treat at last.What this patent was used is the non-homogeneous precipitator method, different with the application's homogeneous coprecipitation method; 80 ℃ of temperature when 75 ℃ of solution temperatures and oven dry precipitated when this patent only provided precipitation do not provide more details.
(6) oxalic acid coprecipitation prepares rare earth doping metal aluminate fluorescent powder (YAG:Tb, SrAl
2O
4: Eu, MgAl
11O
19: Tb, Ce).Relevant document is as follows:
1.Chen TM, Chen SC, Yu CJ.Preparation and characterization of garnet phosphornanoparticles derived from oxalate coprecipitation[J] .Solid State Chem., 1999,144:437-441, this article have set forth the synthetic YAG:Tb fluorescent material of oxalic acid coprecipitation; But dopant ion is Tb, is the pH value of regulating precipitant solution with triethylamine, does not use fusing assistant, does not also compare luminosity.The contriver of present patent application makees YAG:Ce fluorescent material with this method, adopts the elementary operation of above-mentioned document, finds that precipitation is difficult to suction filtration, hard, difficult mill after the oven dry, and the fluorescent material relative brightness behind the sintering is low, may be not suitable for industrialization.
2. Li Xiao cloud, Lu Tianchang, beam is refreshing. the preparation of strontium aluminate long-afterglow luminescent powder and optical property thereof [J]. Nanjing University of Chemical Technology's journal (natural science edition) .2001,21 (3): 563-565, this article have reported with oxalic acid coprecipitation and have got mixed uniformly SrC
2O
4, Al (OH)
3And Eu (OH)
3Precipitation obtains SrAl after the calcining
2O
4: Eu fluorescent material.
3. Li Hong soldier, Liu Younian, Shu Wangen, Lv Xingdong. superfine Mg Al
11O
19: Tb
3+, Ce
3+Preparation research [J]. use chemical industry, 2004,33 (2): 11-13,26, this article has been reported with oxalic acid coprecipitation and has been prepared presoma, prepares green superfine fluorescent powder with the microwave thermal synthesis method again, has studied the factor that influences granularity and luminous intensity.
(7) with the homogeneous oxidizing thing of synthetic yttrium of oxalic acid coprecipitation and cerium, further the homogeneous oxidizing thing of yttrium and cerium is mixed with aluminum oxide and fusing assistant again,, get YAG:Ce fluorescent material through solid state reaction and sintering.Relevant document is as follows:
1. grandson family jumps, Du Haiyan, Hu Wenxiang. solid luminescent material, Beijing: the .2003.394 of chemical press, this book has been narrated the oxalate precipitation that generates yttrium and cerium with oxalate precipitation method, with oxalate precipitation and aluminum oxide and fusing assistant mixing, behind solid state reaction and sintering, make YAG:Ce fluorescent material then.
2. the patent No. is the United States Patent (USP) of US 4034257.This patent report the fluorescent material of YAG:Ce to the effect of the color developing that improves the mercury mercury lamp, and introduced several preparation methods of YAG:Ce fluorescent material: the first adds oxalic acid in the aqueous nitric acid of yttrium and cerium, obtain oxalate precipitation, after calcining the oxide compound that obtains mix with aluminum oxide, fusing assistant ammonium chloride again, by solid state reaction and sintering, make YAG:Ce fluorescent material; It two is with ammoniacal liquor co-precipitation yttrium, aluminium, cerium ion, obtains YAG:Ce fluorescent material after the thermal treatment.
3. the patent No. is the United States Patent (USP) of US 6409938.This patent report generalized YAG:Ce fluorescent material synthetic, and emphasized the effect of fusing assistant aluminum fluoride.The main method that it is introduced is a kind of to be solid phase method; Another kind is first oxalic acid precipitation yttrium, cerium and other rare earth element ion, forms the oxalate compound, forms oxide compound through thermal treatment; Mix with aluminum oxide, fusing assistant aluminum fluoride again, obtain YAG:Ce fluorescent material through pyroprocessing.
4. the patent No. is the Chinese invention patent of ZL 98124953.1.Among the 8th embodiment of this patent, the mixed aqueous solution of preparation Yttrium trinitrate, cerous nitrate and Terbium trinitrate obtains rare-earth oxalate with oxalic acid coprecipitation, through obtain to contain the oxidate powder of yttrium, cerium and terbium 900 ℃ of following thermal treatments; Even with aluminum oxide and barium fluoride mix grinding again, obtain fluorescent material after the pyroprocessing, its chemical formula is (Y
0.949Tb
0.05Ce
0.001)
3Al
5O
12
Summary of the invention
The objective of the invention is to provides the preparation method of a kind of generalized cerium activated yttrium aluminum garnet (YAG:Ce) fluorescent material at the defective of existing preparation YAG:Ce fluorescent material method itself and the difficulty of realization industrialization.Fluorescent material reunion degree after high-temperature heat treatment with this method preparation is low, just can be used for encapsulation without ball milling, can bring into play its excellent optical property to greatest extent.
The molecular formula of cerium activated yttrium aluminium garnet fluorescent powder of the present invention (or being called generalized YAG:Ce) is Y
3-x-y-zR
yAl
5-mGa
mO
12: Ce
x, R '
z, 0.01≤x≤0.12 wherein, R is rare earth elements such as Gd, Sm, 0≤y≤1.20, R ' is a kind of among Pr, the Dy, 0≤z≤0.04,0≤m≤2.00.
The preparation method of cerium activated yttrium aluminium garnet fluorescent powder of the present invention may further comprise the steps:
1) preparation of metal ion solution: press Y
3-x-y-zR
yAl
5-mGa
mO
12: Ce
x, R '
zStoichiometric ratio take by weighing yttrium oxide, gadolinium sesquioxide, Samarium trioxide, dysprosium oxide, the Praseodymium trioxide raw material that purity is 4N and join in the salpeter solution, after the heating for dissolving, add aluminum nitrate (or aluminum chloride), gallium nitrate (or gallium chloride) and cerous nitrate, be mixed with metallic ion mixed liquor;
2) preparation of precipitant solution: take by weighing oxalic acid and be dissolved in the deionized water, heating for dissolving becomes oxalic acid solution, adds ammoniacal liquor again, gets precipitant solution;
3) preparation of precipitation by metallic ion thing: with the metallic ion mixed liquor back titration in precipitant solution, to reacting completely, place ageing after, vacuum filtration, throw out wash with water 1 time at least, with washing with alcohol at least 1 time, obtain white depositions again; Oven dry again, the throw out after must drying;
4) fusing assistant adds and solid state reaction: throw out after will drying and fusing assistant mixed grinding, get white powder, and under reducing atmosphere, ground white powder 800～1250 ℃ of solid state reactions, is got the YAG:Ce powder;
5) sintering: through the YAG:Ce of solid state reaction powder, 1450～1600 ℃ of sintering under reducing atmosphere;
6) will be through the powder of high temperature sintering, after the grinding, pickling successively, alkali cleaning, washing, oven dry, can obtain the luminous intensity height, low without ball milling with regard to the reunion degree, powder diameter is fit to, the target product YAG:Ce fluorescent material of narrow particle size distribution.
In the preparation of metal ion solution, metal ion total concns such as the yttrium of metallic ion mixed liquor, aluminium, cerium are preferably 0.1～0.8mol/L.
In the preparation of precipitant solution, the concentration of oxalic acid solution is preferably 0.1～1.5mol/L, and the consumption of oxalic acid is preferably 1.5～6 times of mole total amount of whole rare earth ions, and the pH value of precipitant solution is preferably 7～10.
In the preparation of precipitation by metallic ion thing, the rate of addition of back titration is preferably 1～4mL/min, and the precipitant solution temperature is preferably 40～75 ℃.Preferably continue to be stirred to after being added dropwise to complete to react completely, the pH value of solution value is preferably 7～9.The temperature of oven dry is preferably 50～120 ℃.
Fusing assistant add and solid state reaction in, fusing assistant is selected from least a in Sodium Fluoride, barium fluoride, aluminum fluoride, Neutral ammonium fluoride, cerium fluoride, the boric acid etc., by mass percentage, the consumption of fusing assistant is 0.5%～6% of a target product YAG:Ce quality.Under reducing atmosphere, ground white powder is preferably 1～6h in the time of 800～1250 ℃ of processing, the optional reduction with carbon protection of reducing atmosphere, or N
2/ H
2Gas mixture is at N
2/ H
2In the gas mixture, by volume, H
2Content be not less than 3% of gas mixture total amount.
In sintering step, the agglomerating time is preferably 1～10h, and reducing atmosphere can be used N
2-H
2Gas mixture.
In step 6), the most well 400 mesh sieves of described grinding, pickling can be adopted dilute nitric acid solution, and alkali cleaning can be adopted dilute ammonia solution.
Compare with traditional solid reaction process, the present invention can make metal ion mix more even, the diffusion distance is shorter, thereby the solid state reaction of making and sintering temperature step-down, time shorten, the result reduced the reunion degree, needn't ball milling, the powder particle crystalline phase of having avoided ball milling to cause is destroyed, luminous intensity reduces.The present invention has overcome that common sol-gel method productive rate is low, second particle is reunited problems such as seriously, easily causing environmental pollution.Except that possessing the advantage that general coprecipitation method prepares YAG:Ce, the invention solves the some shortcomings of general coprecipitation method: oxalate method prepares in the YAG:Ce process, yttrium mainly is that the form with yttrium oxalate is precipitated out, so that the precipitation that generates compares with ammoniacal liquor or the resulting precipitation of bicarbonate of ammonia co-precipitation, easier suction filtration and washing, the also more fluffy easy mill of throw out after the oven dry, the powder after the grinding is thinner, thereby has reduced the fluorescent material preparation cycle and reduced powder particle size.
It should be noted that, the invention solves relevant oxalate precipitation method and do the deficiency of YAG:Ce fluorescent material patent, in the sedimentary while of rare earth ions such as yttrium, make aluminium also precipitate more fully, obtained more uniform throw out, help follow-up solid state reaction and crystal growth process, the relative brightness that has improved fluorescent material significantly.The YAG:Ce fluorescent material D that the present invention at present prepares
50Be 6～9 μ m, the narrow relative brightness of particle size distribution is not less than deep big 432 commodity powder overseas, and the space of further improvement is arranged; And can add other metal ion, make generalized YAG:Ce series phosphor powder.Advantages such as the present invention has that facility investment is few, production technique is simplified, production cost is low, pollute less, good product quality especially are fit to carry out large-scale industrialization production, also are suitable for the preparation of other rare earth doping yttrium aluminium garnet fluorescent powders.
Description of drawings
Fig. 1 is the YAG:Ce fluorescent material sample excitation spectrum and the deep big 432 commodity fluorescent material correlation curve figure of embodiment of the invention preparation.In Fig. 1, X-coordinate is wavelength (nm), and ordinate zou is an intensity, and curve a is the YAG:Ce fluorescent material sample of embodiment of the invention preparation, and curve b is deep big 432 commodity fluorescent material.
Fig. 2 is the YAG:Ce fluorescent material sample emmission spectrum and the deep big 432 commodity fluorescent material correlation curve figure of embodiment of the invention preparation.In Fig. 2, X-coordinate is wavelength (nm), and ordinate zou is an intensity, and curve c is the YAG:Ce fluorescent material sample of embodiment of the invention preparation, and curve d is deep big 432 commodity fluorescent material.
Fig. 3 is the scanning electron microscope picture of the low YAG:Ce fluorescent material sample of certain reunion degree of embodiment of the invention preparation.
(annotate: Fig. 1 and 2 is the test result with the F-4500 of HIT spectrophotofluorometer)
Embodiment
Embodiment 1:Y
2.96Al
5O
12: Ce
0.04The preparation of fluorescent material
Get 3.342g Y
2O
3, joining in the solution that 6.1mL concentrated nitric acid and 100mL deionized water be made into, heating for dissolving is also removed slightly excessive nitric acid; Add 18.757gAl (NO)
39H
2O and 0.174g Ce (NO)
36H
2O, the total concn that is made into metal ion with deionized water is the solution of 0.4mol/L.The oxalic acid that takes by weighing 12.607g is dissolved in the deionized water of 200mL, with ammoniacal liquor adjust pH to 9.5.The mixing solutions of metal-salt constantly is being added drop-wise in the compound precipitants under the stirring condition, is keeping solution temperature at 50 ℃, rate of addition is 2mL/min.Be added dropwise to complete back ageing 12h and refilter, after precipitation spends ionized water, absolute ethanol washing respectively, move into 60 ℃ of dry 12h in the baking oven.Add account for the target product quality be 4.5% NaF as fusing assistant, mixed grinding.Then with precursor under carbon reduction atmosphere at 1150 ℃ of insulation 1h, get final product the YAG:Ce powder of pure phase.Then at N
2/ H
2Under the protection of gas mixture at 1550 ℃ of insulation 3h, get final product good luminous performance, powder diameter be fit to, narrow particle size distribution, nothing is reunited or few YAG:Ce fluorescent material of reuniting.
Embodiment 2:Y
2.94Al
5O
12: Ce
0.06The preparation of fluorescent material
Similar to Example 1, its difference is as follows:
(1) proportioning raw materials is 3.319g Y
2O
3, 18.757g Al (NO
3)
39H
2O and 0.261g Ce (NO
3)
36H
2O; The total concn that is made into metal ion is the solution of 0.3mol/L; The consumption of oxalic acid is 20.171g, is dissolved in 200mL water, adds ammoniacal liquor adjust pH to 9.
(2) the fusing assistant consumption is 1.1% of target product quality, wherein BaF
2And H
3BO
3Respectively account for 0.55%; The temperature of solid state reaction is 1200 ℃, insulation 1h.
(3) carry out high temperature sintering at 1500 ℃ of insulation 4h.
Embodiment 3:Y
2.94Al
4GaO
12: Ce
0.06The preparation of fluorescent material
Similar to Example 1, its difference is as follows:
(1) proportioning raw materials is 3.319g Y
2O
3, 15.006gAl (NO
3)
39H
2O, 2.841g GaCl
36H
2O and 0.261gCe (NO
3)
36H
2O; The total concn that is made into metal ion is the solution of 0.25mol/L.
(2) the fusing assistant consumption is 2% of a target product quality, and wherein NaF accounts for 1.25%, H
3BO
3Account for 0.75%; The temperature of solid state reaction is 1200 ℃, insulation 1h.
Embodiment 4:Y
2.92Al
5O
12: Ce
0.06Pr
0.02The preparation of fluorescent material
Similar to Example 1, its difference is as follows:
(1) proportioning raw materials is 3.297g Y
2O
3, 18.757gAl (NO
3)
39H
2O, 0.087g Pr (NO
3)
36H
2O and 0.261g Ce (NO
3)
36H
2O; The total concn that is made into metal ion is the solution of 0.60mol/L; The consumption of oxalic acid is 15.128g, is dissolved in 300mL water, adds ammoniacal liquor adjust pH to 9.5.
(2) the fusing assistant consumption is 2% of target product quality, wherein BaF
2And H
3BO
3Respectively account for 1%; The temperature of solid state reaction is 1200 ℃, insulation 2h.
Embodiment 5:Y
2.53Gd
0.40Al
5O
12: Ce
0.07The preparation of fluorescent material
Similar to Example 1, its difference is as follows:
(1) proportioning raw materials is 2.856g Y
2O
3, 0.725gGd
2O
3, 18.757g Al (NO
3)
39H
2Ce (the NO of O and 0.305g
3)
36H
2O; The total concn that is made into metal ion is the solution of 0.25mol/L; The consumption of oxalic acid is 8.405g, adds 400mL water, adds ammoniacal liquor adjust pH to 9.
(2) to select the target product quality for use be 0.5%AlF to fusing assistant
3The temperature of solid state reaction is 1250 ℃, insulation 2.5h.
(3) sintering temperature is 1450 ℃, insulation 4h.
Embodiment 6:Y
2.92Al
5O
12: Ce
0.08The preparation of fluorescent material
(1) proportioning raw materials is 3.297g Y
2O
3, 18.757gAl (NO
3)
39H
2O and 0.348g Ce (NO
3)
36H
2O; The total concn that is made into metal ion is the solution of 0.2mol/L; The consumption of oxalic acid is 20.171g, is dissolved in 300mL water, adds ammoniacal liquor adjust pH to 9.
(2) the fusing assistant consumption is the NH of target product quality 1.6%
4F; The temperature of solid state reaction is 1200 ℃, insulation 2h.
Embodiment 7:Y
2.90Al
5O
12: Ce
0.10The preparation of fluorescent material
(1) proportioning raw materials is 3.275g Y
2O
3, 18.757gAl (NO
3)
39H
2O and 0.435g Ce (NO
3)
36H
2O; The total concn that is made into metal ion is the solution of 0.60mol/L; The consumption of oxalic acid is 12.604g, is dissolved in 300mL water, adds ammoniacal liquor adjust pH to 9.
(2) the fusing assistant consumption is 1% of target product quality, wherein CeF
3Account for 0.3%, H
3BO
3Account for 0.7%; At N
2/ H
2950 ℃ of insulations of solid state reaction 1.5h under the mixed atmosphere.
Claims (14)
1. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder, the molecular formula of described cerium activated yttrium aluminium garnet fluorescent powder is Y
3-x-y-zR
yAl
5-mGa
m0
12: Ce
x, R '
z, 0.01≤x≤0.12 wherein, R is rare earth elements such as Gd, Sm, 0≤y≤1.20, R ' is a kind of among Pr, the Dy, 0≤z≤0.04,0≤m≤2.00 is characterized in that may further comprise the steps:
1) preparation of metal ion solution: press Y
3-x-y-zR
yAl
5-mGa
mO
12: Ce
x, R '
zStoichiometric ratio take by weighing yttrium oxide, gadolinium sesquioxide, Samarium trioxide, dysprosium oxide, the Praseodymium trioxide raw material that purity is 4N and join in the salpeter solution, after the heating for dissolving, add aluminum nitrate, gallium nitrate and cerous nitrate, or add aluminum chloride, gallium chloride and cerous nitrate, be mixed with metallic ion mixed liquor;
2) preparation of precipitant solution: take by weighing oxalic acid and be dissolved in the deionized water, heating for dissolving becomes oxalic acid solution, adds ammoniacal liquor again, gets precipitant solution;
3) preparation of precipitation by metallic ion thing: with the metallic ion mixed liquor back titration in precipitant solution, to reacting completely, place ageing after, vacuum filtration, throw out wash with water 1 time at least, with washing with alcohol at least 1 time, obtain white depositions again; Oven dry again, the throw out after must drying;
4) fusing assistant adds and solid state reaction: throw out after will drying and fusing assistant mixed grinding, get white powder, and under reducing atmosphere, ground white powder 800～1250 ℃ of solid state reactions, is got the YAG:Ce powder;
5) sintering: through the YAG:Ce of solid state reaction powder, 1450～1600 ℃ of sintering under reducing atmosphere;
6) will be through the powder of high temperature sintering, after the grinding, pickling successively, alkali cleaning, washing, oven dry, can obtain the luminous intensity height, low without ball milling with regard to the reunion degree, powder diameter is fit to, the target product YAG:Ce fluorescent material of narrow particle size distribution.
2. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder as claimed in claim 1 is characterized in that yttrium, aluminium and the cerium metal total ion concentration of metallic ion mixed liquor is 0.1～0.8mol/L.
3. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder as claimed in claim 1 is characterized in that in the preparation of precipitant solution the concentration of oxalic acid solution is 0.1～1.5mol/L.
4. as the preparation method of claim 1 or 3 described cerium activated yttrium aluminium garnet fluorescent powders, it is characterized in that in the preparation of precipitant solution that the consumption of oxalic acid is 1.5～6 times of mole total amount of whole rare earth ions.
5. as the preparation method of claim 1 or 3 described cerium activated yttrium aluminium garnet fluorescent powders, it is characterized in that in the preparation of precipitant solution that the pH value of precipitant solution is 7～10.
6. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder as claimed in claim 1 is characterized in that in the preparation of precipitation by metallic ion thing the rate of addition of back titration is 1～4mL/min, and solution temperature is 40～75 ℃.
7. as the preparation method of claim 1 or 6 described cerium activated yttrium aluminium garnet fluorescent powders, it is characterized in that in the preparation of precipitation by metallic ion thing that continue to be stirred to after being added dropwise to complete and react completely, the pH value of solution value is 7～9.
8. as the preparation method of claim 1 or 6 described cerium activated yttrium aluminium garnet fluorescent powders, it is characterized in that in the preparation of precipitation by metallic ion thing that the temperature of oven dry is 50～120 ℃.
9. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder as claimed in claim 1, it is characterized in that in fusing assistant interpolation and solid state reaction, fusing assistant is selected from least a in Sodium Fluoride, barium fluoride, aluminum fluoride, Neutral ammonium fluoride, cerium fluoride, the boric acid, by mass percentage, the consumption of fusing assistant is 0.5%～6% of a target product YAG:Ce quality.
10. as the preparation method of claim 1 or 9 described cerium activated yttrium aluminium garnet fluorescent powders, it is characterized in that in fusing assistant interpolation and solid state reaction, under reducing atmosphere, being 1～6h in the time of 800～1250 ℃ of processing with ground white powder.
11., it is characterized in that reducing atmosphere is selected carbon for use, or N in fusing assistant interpolation and solid state reaction as the preparation method of claim 1 or 9 described cerium activated yttrium aluminium garnet fluorescent powders
2/ H
2Gas mixture is at N
2/ H
2In the gas mixture, by volume, H
2Content be not less than 3% of gas mixture total amount.
12. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder as claimed in claim 1 is characterized in that in sintering step, the agglomerating time is 1～10h.
13. the preparation method as claim 1 or 12 described cerium activated yttrium aluminium garnet fluorescent powders is characterized in that in sintering step reducing atmosphere N
2-H
2Gas mixture.
14. the preparation method of cerium activated yttrium aluminium garnet fluorescent powder as claimed in claim 1 is characterized in that in step 6), described 400 mesh sieves that ground.
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