CN101602944A - A kind of production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder - Google Patents

A kind of production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder Download PDF

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CN101602944A
CN101602944A CNA2009101005938A CN200910100593A CN101602944A CN 101602944 A CN101602944 A CN 101602944A CN A2009101005938 A CNA2009101005938 A CN A2009101005938A CN 200910100593 A CN200910100593 A CN 200910100593A CN 101602944 A CN101602944 A CN 101602944A
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rare earth
earth ion
phosphor powder
ion doped
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CN101602944B (en
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夏海平
邱杨
王军
王存宽
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Ningbo University
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Ningbo University
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Abstract

The invention discloses a kind of production method of mixing the rare-earth yttrium-aluminium garnet nano phosphor powder, the general formula of nano-powder is (Y 1-xLn x) 3Al 5O 12, wherein Ln is a kind of of rare earth element ce, Eu, 0.0≤x≤0.1, with the mixing solutions of the nitrate of Al, Y and Ln or acetate as female salts solution, NH 4HCO 3With NH 3H 2The mixing solutions of O is as the composite precipitation agent solution; The pH value of regulating compound precipitants with ammoniacal liquor is 10; Then female salts solution is injected in the composite precipitation agent solution of continuous stirring behind ultrasonic atomizatio, the mixing solutions that reacts completely after filtration, washing, oven dry, repeatedly ball milling, calcining can obtain evenly, the rare earth ion doped YAG nano phosphor powder of dispersive, the advantage of this method be the fluorescent powder that makes evenly, dispersion, granularity little (50～70 nanometer) and resultant be mutually single; Can realize that the high density of rare earth ion evenly mixes, thereby obtain high efficiency rare earth ion doped yttrium aluminum garnet nano phosphor powder.

Description

A kind of production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder
Technical field
The present invention relates to the production method of a kind of yttrium aluminum garnet (YAG) fluorescent powder, particularly a kind of production method of rare earth ion doped yttrium aluminum garnet (YAG) nano phosphor powder.
Background technology
The fluorescent material that with the rare earth ion is luminescence center has obtained a large amount of application in a lot of fields, as lamp phosphor, medical fluorescent material, TV fluorescent material etc., because this added value of product height, remarkable benefit, has become the key areas of rare earth high-tech development.Though the consumption of fluorescent RE powder is less than 4% of the rare earth total quantity consumed, the output value accounts for 41% of rare earth application market total sales volume, is the most popular industry of rare-earth trade [1,2]
Yttrium aluminum garnet (yttrium aluminum garnet), chemical formula is Y 3Al 5O 12, be called for short YAG, have excellent optical property and good mechanical and thermal property, be widely used in laser and luminous host material.Rare earth ion doped YAG fluorescent material is important a kind of in the fluorescent material, YAG as the substrate material of fluorescent material have that transparency height, chemical stability are good, advantage such as good, the anti-high intensity radiation of thermal conductivity and electron-bombardment [3]So rare earth ion doped YAG fluorescent material has obtained extensive studies in recent years.
The preparation method of rare earth ion doped YAG fluorescent material mainly contains high-temperature solid phase reaction method [4], sol-gel method [5], polymer-network gel method [6], solvent-thermal method [7], combustion method [8], spray pyrolysis [9], coprecipitation method [10]Deng, still, all there is certain shortcoming in these methods, and as high-temperature solid phase reaction method, the gained powder needs ball mill pulverizing, and particle is big and size distribution is wide; Sol-gel method needs expensive starting material, cost height; Metal alkoxide in the polymer-network gel method generally is difficult to obtain, and cost is higher, and wants strict control moisture, severe reaction conditions in reaction process; Solvent-thermal method needs higher synthesis temperature and pressure; The powder out-of-shape that combustion method generates; Coprecipitation method is compared with other chemical processes, and that its advantage is is with low cost, equipment simple and be easy to scale operation, but preparation method's process is loaded down with trivial details, processing requirement is harsh, the time is longer.Except that there was certain shortcoming in processing condition, aforesaid method as sol-gel method, was worked as Eu aspect the high-concentration dopant of realizing rare earth ion certain deficiency being arranged also 3+When content reaches 0.06mol, Eu 3+luminously reach the strongest, then along with Eu 3+The concentration quenching phenomenon takes place in the increase of content and reducing [11]Use coprecipitation method, work as Ce 3+Doping content in YAG is 4.8% o'clock, and it is maximum that fluorescence intensity reaches, Ce 3+When doping content further increases, because Ce 3+Between radiationless relaxation and concentration quenching has taken place [12]
Reference:
[1] Lido, river, Yang Yuchun. rare-earth luminescent material new development [J]. rare metal, 1996,20 (2): 129～133.
[2] Wang Yong, Li Ping, Wang Jieqiang. rear-earth-doped YAG fluorescent material preparation method's progress [J]. Shandong chemical industry, 2007,36 (2): 22～27.
[3]CHEN?Teng-Ming，Chen?S?C，Yu?Chao-Jung.Preparation?and?characterization?ofgarnet?phosphor?nanoparticles?derived?from?oxalate?coprecipitation[J].Journal?of?solidstate?chemistry，1999，144：437～441.
[4]Pan?Y?X，Wu?M?M，Su?Q.Tailored?photo-luminescence?of?YAG:Ce?phosphor?thoughvarious?methods[J].J.Phys.Chem.Solids，2000，65：845-850.
[5]H.M.H.Fadlalla，C.C.Tang，E.M.Elssfah，F.Shi.Synthesis?and?characterization?of?singlecrystalline?YAG:Eu?nano-sized?powder?by?sol-gel?method.Materials?Chemistry?andPhysics?109(2008)436-439.
[6]Li?Q，Gao?L，Yan?D?S.Preparation?and?spectra?characterization?of?YAG:Ce 3+?ultrafinepowders.J.Inorg.Mater，1997，12(4)：575-578.
[7]Xia?Li，Qiang?Li，Jiyang?Wang，Shunliang?Yang.Synthesis?of?YAG:Eu?phosphors?withspherical?morphology?by?solvo-thermal?method?and?their?luminescent?property.MaterialsScience?and?Engineering?B?131(2006)32-35
[8] Xia Guodong, Zhou Shengming, Zhang Junji, Zhang Lianhan, Jia Guangqiang Xu Jun. gel-combustion method is synthesized YAG:Eu 3+The structure of nano-luminescent material and luminescent properties. Chinese Journal of Inorganic Chemistry, 2005,21 (8): 1203-1207.
[9]Y.H.Zhou，J.Lin，M.Yu，S.M.Han，S.B.Wang，H.J.Zhang.Morphology?control?andluminescence?properties?of?YAG:Eu?phosphors?prepared?by?spray?pyrolysis.MaterialsResearch?Bulletin?38(2003)1289-1299.
[10]J.Su，Q.L.Zhang，S.F.Shao，W.P.Liu，S.M.Wan，S.T.Yin.Phase?transition，structureand?luminescence?of?Eu:YAG?nanophosphors?by?co-precipitation?method.Journal?ofAlloys?and?Compounds，2008.
[11] the week oath is red, Zhang Siyuan, Zhang Jingjun, Pan Wenge .YAG:Eu 3+, Bi 3+Sol-gel method synthetic and structure and luminous. SCI .1998,19 (11): 1826-1828.
[12] Zhang Kai, Liu Hezhou, the coroner Asia is graceful, Hu Wenbin. and coprecipitation method prepares nanometer cerium doped yttrium aluminum garnet fluorescent powder and fluorescent characteristic thereof. mechanical engineering material .2007,31 (1): 53-56.
Summary of the invention
Technical problem to be solved by this invention provides a kind of epigranular, dispersion and generates the production method of yttrium aluminum garnet (YAG) nano phosphor powder of mutually single, high-concentration dopant rare earth ion, this method equipment is simple, easy to operate, the combined coefficient height, the doping content height of particle diameter of nanometer powder narrow distribution range, degree of crystallinity and the rare earth ion of production.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder, and it may further comprise the steps:
The general formula of 1. rare earth ion doped yttrium aluminum garnet is (Y 1-χLn χ) 3Al 5O 12, wherein Ln is a kind of among rare earth element ce, the Eu, its doping χ is 0.01≤χ≤0.1, according to the stoichiometric ratio of general formula, is raw material with their corresponding nitrate or acetate, makes mixed aqueous solution as female salts solution, cofabrication NH 4HCO 3The aqueous solution is used NH 3H 2O regulates NH 4HCO 3PH value of aqueous solution to 10 will add NH 3H 2NH behind the O 4HCO 3Solution is as precipitant solution;
2. female salts solution is injected in the precipitant solution through behind the ultrasonic atomizatio, the control mist flow makes to be reflected in 1～15h to be finished, and carries out mechanical stirring in the liquid of hybrid reaction simultaneously;
3. the mixing solutions that will react filters, and then the material after filtering is washed, and uses washed with de-ionized water earlier, cleans with dehydrated alcohol again;
4. cleaned material is put into oven drying, drying temperature is 90～130 ℃, time of drying 6～20h;
5. dried material is dispersed in the dehydrated alcohol, carries out repetitious wet-milling with the Ceramic Balls of different size size respectively, dry again after the wet-milling, and then repeatedly dry grind with the Ceramic Balls of different size size and to obtain powder;
6. the powder after will dry grinding promptly obtains rare earth ion doped nano phosphor powder at 900～1200 ℃ of temperature sintering 1～5h.
The female salts solution of described step in 1. is the nitrate of Al, Y and Ln or the mixing solutions of acetate, and its positively charged ion total concn is 0.1～0.5 mol; NH 4HCO 3The concentration of the aqueous solution is 0.1～1 mol, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1.
The ultrasonic atomizatio of described step in 2. is at room temperature, liquid stream is that it is 40～600 milliliters/hour that regulated valve makes flow rate of liquid, in the 50KHz frequency behind 0.1～0.6 millimeter the shower nozzle through internal diameter, under the ultrasonication of 10～80W continuous output, be transformed into little mist vapour; The distance of regulating nozzle and reaction liquid level makes the contact reacts area of little mist vapour and liquid level at least greater than 15m 2, churned mechanically rotating speed is 20～200 rev/mins.
The wet-milling of described step in 5. is to use earlier Φ 25mm, use Φ 10mm again, with zirconia ball difference ball milling 0.5～8h of Φ 5mm, the add-on of dehydrated alcohol is 5～50 milliliters of every gram materials at last, after the described wet-milling again the exsiccant temperature be 110～130 ℃, be 10～20h time of drying; Described dry grinding is with zirconia ball ball milling 0.5～8h of Φ 25mm, uses Φ 10mm again, uses each ball milling 0.5～3h of zirconia ball of Φ 5mm at last.
Compared with prior art, the invention has the advantages that the method that adopts ullrasonic spraying and co-precipitation to combine carries out the production of rare earth ion doped yttrium aluminum garnet nano phosphor powder.
Coprecipitation method is to add suitable precipitation agent in blended metal salt solution (metal ion that contains two or more), and reaction generates forms precipitation uniformly, and precipitation heat obtains high-purity superfine powdery material after decomposing.The characteristics of coprecipitation method maximum are: the solution nucleation is fast, and is easy to control, can make highly purified product, the nano powder that can be uniformly dispersed, size-grade distribution is narrow; This method equipment is simple, is easy to industrialization, has stronger industrial promotional value.But coprecipitation method has following serious defective, promptly easily reunites in precipitation process, and particle diameter is wayward, and particle radius is big.
And ullrasonic spraying is to utilize the ultrasonic cavitation energy to quicken and the control chemical reaction, improve a kind of new technology of the new chemical reaction of reaction yield and initiation, the inventor utilizes the ultrasonic cavitation energy, female salts solution of reaction is changed into the little vaporific drop with certain energy and big area is sprayed onto in the co-precipitation mixing solutions, and transforming the little mist vapour that obtains is a kind of evenly tiny liquid small-particle.The mother liquor of handling through ultrasonic atomizatio, carry out chemical reaction with the composite precipitation agent solution after, be expected to improve the homogeneity of chemical reaction, obtain tiny, dispersive nano-powder.
And the production method that combines above-mentioned two kinds of technology obviously has following characteristics: 1. female salts solution is at first handled through ultrasonic atomizatio, make it become little mist vapour with certain energy, big area is ejected in the mixed precipitation agent solution, thereby increased the homogeneity of chemical reaction, phenomenons such as nanoparticle agglomerates have been overcome, the particle granularity that obtains after the calcining only is 50～70 nanometer (see figure 1)s, and powder is single YAG phase (see figure 2); 2. another characteristics of the present invention are rear-earth-doped YAG not to be had the treatment technology of reunion fluorescent powder.Conventional all fairly simple to the processing and the store method of rear-earth-doped YAG fluorescent powder, usually the shelf time not long, cause the particulate hard aggregation easily.We pass through the repeatedly wet-milling and the dry grinding repeatedly of coupling different size Ceramic Balls, obtain good dispersion, the evenly interior single rear-earth-doped YAG fluorescent powder (see figure 1) of seldom reuniting; 3. the YAG powder that method of the present invention is produced also has beyond thought high concentration rare earth doping characteristic, has very high concentration quenching effect, in the YAG:Eu powder, quenching of fluorescence phenomenon (Fig. 4) does not appear, apparently higher than the 6mol% of sol-gel method when the Eu doping content reaches 10mol%.In the YAG:Ce powder, when the Ce doping content reached 6～7mol%, fluorescence intensity reached maximum (see figure 6), apparently higher than the 4.8mol% of coprecipitation method.Therefore use this method can realize high efficiency rare earth ion doped YAG nano phosphor powder.
Description of drawings
Fig. 1 is the SEM figure of the YAG:Ln sample of 1000 ℃ of calcining 2h, (a) Ln=Eu; (b) Ln=Ce.;
Fig. 2 is the XRD figure of YAG:Ln (Ln=Eu, Ce) presoma at differing temps calcining 2h;
Fig. 3 is the emmission spectrum of the YAG:Eu powder of different Eu doping contents, (1) 1%Eu; (2) 2%Eu; (3) 4%Eu; (4) 6%Eu; (5) 8%Eu; (6) 10%Eu.;
Fig. 4 is the emissive porwer (λ of different levels of doping Eu:YAG powder Ex=396nm);
Fig. 5 is the emmission spectrum of the YAG:Ce powder of various ce doping content, (1) 1%Ce; (2) 2%Ce; (3) 4%Ce; (4) 6%Ce; (5) 8%Ce; (6) 10%Ce.;
Fig. 6 is the emissive porwer (λ of different levels of doping Ce:YAG powder Ex=470nm).
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment 1:
(1) at first with Al (NO 3) 3, Y (NO 3) 3And Eu (NO 3) 3Solution is according to general formula (Y 0.98Eu 0.02) 3Al 5O 12Stoichiometric ratio, being made into cation concn is female salts solution of 0.2 mol, prepares the ammonium bicarbonate solution of 0.6 mol again with deionized water, and with the pH to 10 of ammoniacal liquor regulator solution, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1;
(2) regulated valve, making female salts solution aperture of flowing through is 0.20 millimeter titanium alloy ullrasonic spraying head, flow velocity with 300 milliliters/hour enters ultrasonic atomizing device, the control mist flow makes to be reflected in 4 hours to be finished, under the continuous ultrasound effect of frequency 50KHz, power 45W, join behind the ultrasonic atomizatio in the mixed precipitation agent solution of continuous stirring, the spray reaction area is about 35cm 2Mechanical stirring speed is 80 rev/mins;
(3) will mix object and filter, the material that obtains is used washed with de-ionized water 1 time earlier, cleans 3 times with dehydrated alcohol again;
(4) material that will clean is put into baking oven, and temperature remains on 120 ℃ of dry 12h;
(5) drying is good material is dispersed in the dehydrated alcohol, and the add-on of dehydrated alcohol is 10 milliliters of every gram materials, uses Φ 25mm earlier, uses Φ 10mm again, uses each ball milling 2h of zirconia ball of Φ 5mm at last; Then that ball milling is good powder is placed on dry 12h in the baking oven that temperature remains on 120 ℃; Use the zirconia ball ball milling 1h of Φ 25mm after the drying again, use Φ 10mm again, use each ball milling 1h of zirconia ball of Φ 5mm at last;
(6) powder after will dry grinding promptly obtains rare earth ion doped YAG nano phosphor powder at 1000 ℃ of temperature lower calcination 2h.
Embodiment 2:
(1) at first with Al (NO 3) 3, Y (NO 3) 3And Ce (NO 3) 3Solution is according to general formula (Y 0.96Ce 0.04) 3Al 5O 12Stoichiometric ratio be made into female salts solution that cation concn is 0.3 mol, prepare the ammonium bicarbonate solution of 0.9 mol again with deionized water, and with the pH to 10 of ammoniacal liquor regulator solution, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1;
(2) regulated valve, making female salts solution aperture of flowing through is 0.20 millimeter titanium alloy ullrasonic spraying head, flow velocity with 300 milliliters/hour enters ultrasonic atomizing device, the control mist flow makes to be reflected in 4 hours to be finished, under the continuous ultrasound effect of frequency 50KHz, power 45W, join behind the ultrasonic atomizatio in the mixed precipitation agent solution of continuous stirring, the spray reaction area is about 35cm 2Mechanical stirring speed is 80 rev/mins;
(3) will mix object and filter, the material that obtains is used washed with de-ionized water 1 time earlier, cleans 3 times with dehydrated alcohol again;
(4) material that will clean is put into baking oven, and temperature remains on 120 ℃ of dry 12h;
(5) drying is good material is dispersed in the dehydrated alcohol, and the add-on of dehydrated alcohol is 10 milliliters of every gram materials, uses Φ 25mm earlier, uses Φ 10mm again, uses each ball milling 2h of zirconia ball of Φ 5mm at last; Then that ball milling is good powder is placed on dry 12h in the baking oven that temperature remains on 120 ℃; Use the zirconia ball ball milling 1h of Φ 25mm after the drying again, use Φ 10mm again, use each ball milling 1h of zirconia ball of Φ 5mm at last;
(6) powder after will dry grinding promptly obtains rare earth ion doped YAG nano phosphor powder at 1000 ℃ of temperature sintering 2h.
Embodiment 3:
(1) at first with Al (Ac) 3, Y (Ac) 3And Eu (Ac) 3Solution is according to general formula (Y 0.94Eu 0.06) 3Al 5O 12Stoichiometric ratio be made into female salts solution that cation concn is 0.15 mol, prepare the ammonium bicarbonate solution of 0.45 mol again with deionized water, and with the pH to 10 of ammoniacal liquor regulator solution, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1;
(2) regulated valve, making female salts solution aperture of flowing through is 0.20 millimeter titanium alloy ullrasonic spraying head, flow velocity with 200 milliliters/hour enters ultrasonic atomizing device, the control mist flow makes to be reflected in 4 hours to be finished, under the continuous ultrasound effect of frequency 50KHz, power 45W, join behind the ultrasonic atomizatio in the mixed precipitation agent solution of continuous stirring, the spray reaction area is about 35cm 2Mechanical stirring speed is 80 rev/mins;
(3) will mix object and filter, the material that obtains is used washed with de-ionized water 1 time earlier, cleans 3 times with dehydrated alcohol again;
(4) material that will clean is put into baking oven, and temperature remains on 120 ℃ of dry 12h;
(5) drying is good material is dispersed in the dehydrated alcohol, and the add-on of dehydrated alcohol is 15 milliliters of every gram materials, uses Φ 25mm earlier, uses Φ 10mm again, uses each ball milling 2h of zirconia ball of Φ 5mm at last; Then that ball milling is good powder is placed on dry 12h in the baking oven that temperature remains on 120 ℃; Use the zirconia ball ball milling 1h of Φ 25mm after the drying again, use Φ 10mm again, use each ball milling 1h of zirconia ball of Φ 5mm at last;
(6) powder after will dry grinding promptly obtains rare earth ion doped YAG nano phosphor powder at 1000 ℃ of temperature sintering 2h.
Embodiment 4:
(1) at first with Al (NO 3) 3, Y (NO 3) 3And Eu (NO 3) 3Solution is according to general formula (Y 0.96Eu 0.04) 3Al 5O 12Stoichiometric ratio be made into female salts solution that cation concn is 0.25 mol, prepare the ammonium bicarbonate solution of 0.75 mol again with deionized water, and with the pH to 10 of ammoniacal liquor regulator solution, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1;
(2) regulated valve, making female salts solution aperture of flowing through is 0.15 millimeter titanium alloy ullrasonic spraying head, flow velocity with 100 milliliters/hour enters ultrasonic atomizing device, the control mist flow makes to be reflected in 4 hours to be finished, under the continuous ultrasound effect of frequency 50KHz, power 20W, join behind the ultrasonic atomizatio in the mixed precipitation agent solution of continuous stirring, the spray reaction area is about 20cm 2Mechanical stirring speed is 100 rev/mins;
(3) will mix object and filter, the material that obtains is used washed with de-ionized water 1 time earlier, cleans 3 times with dehydrated alcohol again;
(4) material that will clean is put into baking oven, and temperature remains on 100 ℃ of dry 15h;
(5) drying is good material is dispersed in the dehydrated alcohol, and the add-on of dehydrated alcohol is 20 milliliters of every gram materials, uses Φ 25mm earlier, uses Φ 10mm again, uses each ball milling 3h of zirconia ball of Φ 5mm at last; Then that ball milling is good powder is placed on dry 15h in the baking oven that temperature remains on 100 ℃; Use the zirconia ball ball milling 1.5h of Φ 25mm after the drying again, use Φ 10mm again, use each ball milling 1h of zirconia ball of Φ 5mm at last;
(6) powder after will dry grinding promptly obtains rare earth ion doped YAG nano phosphor powder at 900 ℃ of temperature sintering 3h.
Embodiment 5:
(1) at first with Al (Ac) 3, Y (Ac) 3And Ce (Ac) 3Solution is according to general formula (Y 0.94Ce 0.06) 3Al 5O 12Stoichiometric ratio be made into female salts solution that cation concn is 0.2 mol, prepare the ammonium bicarbonate solution of 0.6 mol again with deionized water, and with the pH to 10 of ammoniacal liquor regulator solution, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1;
(2) regulated valve, making female salts solution aperture of flowing through is 0.45 millimeter titanium alloy ullrasonic spraying head, flow velocity with 450 milliliters/hour enters ultrasonic atomizing device, the control mist flow makes to be reflected in 4 hours to be finished, under the continuous ultrasound effect of frequency 50KHz, power 40W, join behind the ultrasonic atomizatio in the mixed precipitation agent solution of continuous stirring, the spray reaction area is about 22cm 2Mechanical stirring speed is 90 rev/mins;
(3) will mix object and filter, the material that obtains is used washed with de-ionized water 1 time earlier, cleans 3 times with dehydrated alcohol again;
(4) material that will clean is put into baking oven, and temperature remains on 130 ℃ of dry 8h;
(5) drying is good material is dispersed in the dehydrated alcohol, and the add-on of dehydrated alcohol is 30 milliliters of every gram materials, uses Φ 25mm earlier, uses Φ 10mm again, uses each ball milling 4.5h of zirconia ball of Φ 5mm at last; Then that ball milling is good powder is placed on dry 8h in the baking oven that temperature remains on 130 ℃; Use the zirconia ball ball milling 2h of Φ 25mm after the drying again, use Φ 10mm again, use each ball milling 1h of zirconia ball of Φ 5mm at last;
(6) powder after will dry grinding promptly obtains rare earth ion doped YAG nano phosphor powder at 1100 ℃ of temperature sintering 1.5h.

Claims (4)

1, a kind of production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder is characterized in that it may further comprise the steps:
The general formula of 1. rare earth ion doped yttrium aluminum garnet is (Y 1-χLn χ) 3Al 5O 12, wherein Ln is a kind of among rare earth element ce, the Eu, its doping χ is 0.01≤χ≤0.1, according to the stoichiometric ratio of general formula, is raw material with their corresponding nitrate or acetate, makes mixed aqueous solution as female salts solution, cofabrication NH 4HCO 3The aqueous solution is used NH 3H 2O regulates NH 4HCO 3PH value of aqueous solution to 10 will add NH 3H 2NH behind the O 4HCO 3Solution is as precipitant solution;
2. female salts solution is injected in the precipitant solution through behind the ultrasonic atomizatio, the control mist flow makes to be reflected in 1～15h to be finished, and carries out mechanical stirring in the liquid of hybrid reaction simultaneously;
3. the mixing solutions that will react filters, and then the material after filtering is washed, and uses washed with de-ionized water earlier, cleans with dehydrated alcohol again;
4. cleaned material is put into oven drying, drying temperature is 90～130 ℃, time of drying 6～20h;
5. dried material is dispersed in the dehydrated alcohol, carries out repetitious wet-milling with the Ceramic Balls of different size size respectively, dry again after the wet-milling, and then repeatedly dry grind with the Ceramic Balls of different size size and to obtain powder;
6. the powder after will dry grinding promptly obtains rare earth ion doped nano phosphor powder at 900～1200 ℃ of temperature sintering 1～5h.
2, the production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder according to claim 1, it is characterized in that the female salts solution during described step 1. is the nitrate of Al, Y and Ln or the mixing solutions of acetate, its positively charged ion total concn is 0.1～0.5 mol; NH 4HCO 3The concentration of the aqueous solution is 0.1～1 mol, NH 4HCO 3Molar weight and (Y 1-χLn χ) 3Al 5O 12The ratio of middle positively charged ion integral molar quantity is 3: 1.
3, the production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder according to claim 1, it is characterized in that the ultrasonic atomizatio during described step 2. is at room temperature, liquid stream is behind 0.1～0.6 millimeter the shower nozzle through internal diameter, it is 40～600 milliliters/hour that regulated valve makes flow rate of liquid, in the 50KHz frequency, under the ultrasonication of 10～80W continuous output, be transformed into little mist vapour; The distance of regulating nozzle and reaction liquid level makes the contact reacts area of little mist vapour and liquid level at least greater than 15m 2, churned mechanically rotating speed is 20～200 rev/mins.
4, the production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder according to claim 1, it is characterized in that the wet-milling during described step 5. is to use earlier Ф 25mm, use Ф 10mm again, use zirconia ball difference ball milling 0.5～8h of Ф 5mm at last, the add-on of dehydrated alcohol is 5～50 milliliters of every gram materials, after the described wet-milling again the exsiccant temperature be 110～130 ℃, be 10～20h time of drying; Described dry grinding is with zirconia ball ball milling 0.5～8h of Ф 25mm, uses Ф 10mm again, uses each ball milling 0.5～3h of zirconia ball of Ф 5mm at last.
CN2009101005938A 2009-07-09 2009-07-09 Method for producing rare earth ion doped yttrium aluminum garnet nano phosphor powder Expired - Fee Related CN101602944B (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CZ302642B6 (en) * 2010-06-18 2011-08-10 Ceské vysoké ucení technické v Praze Fakulta jaderná a fyzikálne inženýrská Process for preparing powder ceramic material Y3AI5O12 (YAG)
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CZ302642B6 (en) * 2010-06-18 2011-08-10 Ceské vysoké ucení technické v Praze Fakulta jaderná a fyzikálne inženýrská Process for preparing powder ceramic material Y3AI5O12 (YAG)
CN103361059A (en) * 2013-07-26 2013-10-23 莆田学院 Ammonia homogeneous precipitation method for preparing Ce-doped yttrium aluminum garnet phosphor
CN103525422A (en) * 2013-09-26 2014-01-22 苏州微之陶新材料有限公司 Fluorescent powder used for white-light LED (light emitting diode) and preparation method of fluorescent powder
CN104045103A (en) * 2014-06-24 2014-09-17 中国工程物理研究院化工材料研究所 Yttrium aluminium garnet nano-powder and preparation method thereof
CN105602563A (en) * 2016-03-14 2016-05-25 宁波江东索雷斯电子科技有限公司 Preparation method of yttrium-aluminum-garnet-doped rare-earth high-luminance fluorescent powder
CN107384311A (en) * 2017-06-03 2017-11-24 安徽绿环泵业有限公司 A kind of flange lapping liquid for being used to improve membrane pump sealing
CN107999255A (en) * 2017-12-05 2018-05-08 连云港隆和矿产有限公司 A kind of efficiently water process garnet filtrate production technology
CN111018513A (en) * 2019-12-30 2020-04-17 江苏师范大学 Preparation method of fluorapatite complex-phase fluorescent ceramic material for high-luminous-efficiency LED/LD illumination
WO2022134040A1 (en) * 2020-12-25 2022-06-30 苏州君诺新材科技有限公司 Preparation method for eu2+ ion doped yttrium aluminum garnet structure fluorescent powder
CN112661185A (en) * 2021-01-13 2021-04-16 安徽理工大学环境友好材料与职业健康研究院(芜湖) Preparation method of niobate nanotube with one-dimensional tubular structure

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