CN107686345B - Preparation method of Ce-doped YAG luminescent ceramic - Google Patents
Preparation method of Ce-doped YAG luminescent ceramic Download PDFInfo
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Abstract
The invention discloses a preparation method of Ce-doped YAG luminescent ceramic, which comprises the following steps: reacting yttrium oxide nano powder with a soluble cerium salt solution in the presence of a precipitator to generate a precursor of coated yttrium oxide-cerium oxide composite powder, and roasting to obtain the coated yttrium oxide-cerium oxide composite powder with cerium oxide coated on the surface of the yttrium oxide nano powder; and mixing the yttrium oxide-cerium oxide composite powder with an aluminum compound, and then carrying out pretreatment sintering and sintering to obtain the Ce-doped YAG luminescent ceramic. Cerium in the coated yttrium oxide-cerium oxide composite powder obtained by the preparation method is fully and uniformly contacted with yttrium oxide, so that the reaction efficiency of cerium entering yttrium crystal lattices is improved, and the phase purity of luminescent ceramic is improved; meanwhile, the preparation method has the advantages of simple process, shortened production period and reduced cost, and is suitable for batch production.
Description
Technical Field
The invention relates to the technical field of YAG luminescent ceramics, in particular to a preparation method of Ce-doped YAG luminescent ceramics based on coated yttrium oxide-cerium oxide composite powder.
Background
With the rapid development of the semiconductor light source industry, the application of light sources with high power, small light spots and ultrahigh brightness is more and more extensive, and the high power density of the exciting light is difficult to bear by adopting silica gel to package the excited light of the fluorescent powder material. At present, transparent glass materials are used as binders for packaging fluorescent powder most commonly, but the fluorescent powder is subjected to thermal saturation due to high heat accumulation caused by high power, and the luminance attenuation is obvious after long-term use, and the main reasons are that the heat conductivity of glass is poor and the heat dissipation effect is general.
For this reason, efforts have been made to study Ce-doped YAG luminescent ceramics, which have the structural property that cerium substitutes for part of the lattice sites of yttrium. The preparation method of the Ce-doped YAG luminescent ceramic usually adopts a solid phase method. In the solid phase process, the incorporation of cerium (Ce) is a critical point, and is generally incorporated in the form of cerium oxide. Because the doping amount is less, the mixed materials between solid phases are difficult to uniformly disperse, and in the preparation of Ce doped YAG by solid-solid reaction, a plurality of defects, incomplete reaction and the like exist. The expression is as follows: on one hand, the crystal lattice distribution of cerium in yttrium is not uniform, the cerium content in local areas is higher, and the luminous concentration is quenched; on the other hand, the phase purity of the luminescent ceramics is low, and many mesophase products exist. The above problems directly affect the luminous efficiency of the luminescent ceramic.
The key point for improving the fluorescence efficiency of the Ce-doped YAG luminescent ceramic is to improve the cerium doping uniformity, improve the dispersion performance of cerium in a solid phase method mixed material and improve the phase purity of the luminescent ceramic. The method has the advantages that cerium is added into a raw material formula in a liquid phase form, nitrate of cerium, yttrium and aluminum is mixed and precipitated together in a liquid phase to prepare the Ce-doped YAG precursor powder by a traditional coprecipitation method, the problem of uneven mixing is solved, a large amount of salt solution and acid-base solution need to be prepared, the preparation process is complex, the period is long, more waste acid-base salt solution is needed, the environmental pollution is serious, and the corrosion to equipment is strong.
Disclosure of Invention
The invention provides a preparation method of Ce-doped YAG luminescent ceramic based on coated yttrium oxide-cerium oxide composite powder, which has simple process, only needs a small amount of acid-base salt solution and has no pollution to the environment.
The invention is realized by the following technical scheme:
a preparation method of Ce-doped YAG luminescent ceramic comprises the following steps:
(1) preparing yttrium oxide-cerium oxide composite powder: reacting yttrium oxide nano powder with a soluble cerium salt solution in the presence of a precipitator to generate a precursor of coated yttrium oxide-cerium oxide composite powder, and roasting to obtain the coated yttrium oxide-cerium oxide composite powder with cerium oxide coated on the surface of the yttrium oxide nano powder;
(2) preparing Ce-doped YAG luminescent ceramic: and mixing the yttrium oxide-cerium oxide composite powder with an aluminum compound, and then carrying out sintering pretreatment and sintering to obtain the Ce-doped YAG luminescent ceramic.
Wherein, the first scheme is carried out in the presence of a precipitating agent, and the specific steps comprise:
(a) preparing yttrium oxide nano powder suspension: adding the pretreated yttrium oxide nano powder into the solution of the first precipitator, and uniformly dispersing to obtain uniform suspension;
(b) preparing a soluble cerium salt solution: adding a predetermined amount of soluble cerium salt into water to obtain a soluble cerium salt solution;
(c) deposition and coating: slowly dripping the cerium salt solution into the suspension, stirring and aging to obtain a mixed solution, washing and drying the mixed solution to obtain a precursor of the coated yttrium oxide-cerium oxide composite powder;
(d) roasting a precursor: and roasting the precursor of the coated yttrium oxide-cerium oxide composite powder to obtain the coated yttrium oxide-cerium oxide composite powder.
Further, the yttrium oxide nanopowder and the soluble cerium salt are prepared according to the ratio (1-x)/x of the amount of yttrium substance to the amount of cerium substance, wherein 0< x < 0.1.
Further, the first precipitant is a soluble bicarbonate.
Further, the first precipitator is NH4HCO3The concentration of the solution is 0.01-2 mol/L.
Further, the cerium salt solution is slowly added dropwise into the suspension under the heating condition of water bath.
The second scheme is carried out in the presence of a precipitating agent, and comprises the following specific steps:
(a) preparing a soluble cerium salt solution: adding a predetermined amount of soluble cerium salt into water to obtain a cerium salt solution;
(b) preparing a suspension: adding the pretreated yttrium oxide nano powder into the cerium salt solution to obtain a suspension;
(c) coating with sol-gel: dropwise adding a second precipitator into the suspension, uniformly dispersing to obtain a mixed suspension, washing, drying, and grinding to obtain a precursor of the coated yttrium oxide-cerium oxide composite powder;
(d) roasting a precursor: and roasting the precursor of the coated yttrium oxide-cerium oxide composite powder to obtain the coated yttrium oxide-cerium oxide composite powder.
Further, the yttrium oxide nanopowder and the soluble cerium salt are prepared according to the ratio (1-x)/x of the amount of yttrium substance to the amount of cerium substance, wherein 0< x < 0.1.
Further, the second precipitator includes hydrogen peroxide and an aqueous ammonia solution.
Further, the concentration of the hydrogen peroxide is 0.1-1mol/L, and the concentration of the ammonia water solution is 0.1-1 mol/L.
Further, the aluminum compound includes at least one of aluminum oxide, aluminum hydroxide, aluminum nitrate, aluminum sulfate, and aluminum carbonate.
Compared with the prior art, the method adopts a liquid phase method to pretreat yttrium oxide powder in YAG raw material powder, coats cerium oxide on the surface of the yttrium oxide powder, obtains a coated yttrium oxide-cerium oxide composite powder material after roasting, mixes the powder material with aluminum oxide powder, and obtains the Ce-doped YAG luminescent ceramic after a series of processing processes. In the coated yttrium oxide-cerium oxide composite powder obtained by the preparation method, cerium and yttrium oxide can be fully and uniformly contacted with each other, the dispersion performance of cerium in a solid phase method mixed material is improved, and the reaction efficiency of cerium entering yttrium crystal lattices is improved, so that the phase purity of luminescent ceramics is improved.
Drawings
FIG. 1 is a schematic process flow diagram in one embodiment of the present invention;
FIG. 2 is a schematic process flow diagram of another embodiment of the present invention.
Detailed Description
In the invention, the preparation method of the yttrium oxide-cerium oxide composite powder adopts the whole thought of a liquid phase method.
The first scheme principle is that the first precipitator reacts with cerium salt to generate precipitate, the cerium salt precipitate is attached to yttrium oxide nano powder and decomposed into cerium oxide after being roasted, and the coating effect is realized. In one embodiment of the present invention, the specific steps are as follows:
pretreatment of yttrium oxide: and (3) carrying out ultrasonic cleaning on the yttrium oxide nano powder by absolute ethyl alcohol, ultrasonic cleaning by a low-concentration alkali solution and repeated cleaning by deionized water, and drying for later use. In the ultrasonic cleaning of the low-concentration alkali solution, NaOH solution or other alkali solutions can be used. Although non-pretreated yttria can also be used in the present invention, the inventors have noted that pretreated yttria can achieve better results. The reason is that through ultrasonic cleaning, especially cleaning of NaOH solution or other alkaline solutions, oxide impurities on the surface of the yttrium oxide nano powder are removed, the surface activity of the yttrium oxide nano powder is enhanced, and the coating effect and the dispersion effect are better.
Preparing a suspension: weighing a predetermined amount of NH4HCO3Dissolving in deionized water to obtain 0.01-2mol/L NH4HCO3Adding a predetermined amount of yttrium oxide nano powder into the solution, mechanically stirring for a period of time, and then ultrasonically dispersing for a period of time to obtain uniform yttrium oxide nano powder suspension. Wherein the order of ultrasonic dispersion and mechanical stirring dispersion can be switched. NH (NH)4HCO3The solution is used as the first precipitant, which in other embodiments may be other soluble bicarbonate salts. The first precipitator has the action principle that bicarbonate radical in the first precipitator reacts with cerium salt to generate cerium bicarbonate precipitate.
Preparing a soluble cerium salt solution: according to the chemical formula 3(1-x)/2Y2O3+2.5Al2O3+3xCeO2→(Y1-xCex)3Al5O12Wherein 0 is<x<0.1 gives a Y/Ce molar ratio of (1-x)/x, where 0<x<0.1. Weighing a certain amount of Ce (NO) according to the molar ratio of Y to Ce3)3·6H2Dissolving O in deionized water, and mechanically stirring to obtain Ce (NO)3)·6H2And completely dissolving the O to obtain a soluble cerium salt solution. In other embodiments, other soluble cerium salts may be used instead of Ce (NO)3)4E.g. Ce2(SO4)3·8H2O、CeX3·6H2O(X＝F、Cl、Br、I)、Ce2(SO4)3·8H2O、CeX3·6H2And O (X ═ F, Cl, Br, I), and the like.
Deposition and coating: pouring the suspension into a round-bottom flask, placing the round-bottom flask in a water tank of constant-temperature water bath (for example, constant temperature of 60-80 ℃, preferably 60 ℃), mechanically stirring at a certain rotating speed, slowly dripping the cerium salt solution into the suspension at a certain dripping speed by using a peristaltic pump, continuing stirring for a period of time after dripping, stopping stirring, and aging for a certain period of time to obtain a mixed solution. And (3) carrying out suction filtration and water washing on the mixed solution for a plurality of times, dehydrating the mixed solution for a plurality of times by using absolute ethyl alcohol, and then placing the dehydrated mixed solution in an oven for drying for a certain time to obtain a precursor of the coated yttrium oxide-cerium oxide composite powder.
Roasting a precursor: and putting the precursor of the coated yttrium oxide-cerium oxide composite powder into a muffle furnace at a certain temperature for roasting for several hours to obtain the faint yellow coated yttrium oxide-cerium oxide composite powder.
After the yttrium oxide-cerium oxide composite powder is obtained, the Ce-doped YAG luminescent ceramic can be continuously prepared by the following steps.
Ball milling and mixing: the mass of the aluminum compound required is calculated according to the molar amount of Al obtained from the molar ratio of Ce/Al or Y/Al in the above chemical formula, the aluminum compound can be at least one of alumina, aluminum hydroxide, aluminum nitrate, aluminum sulfate and aluminum carbonate, the aluminum compound can obtain alumina at high temperature, for example, the aluminum hydroxide can obtain alumina and water at high temperature. Adding yttrium oxide-cerium oxide composite powder and aluminum compound into a ball milling tank, and adding Al which is several times of the total powder mass2O3Balls or ZrO2And adding ethanol into the ball, and performing ball milling for several hours.
Preparing the ceramic: ball-milling the mixed powder, and sintering to obtain the Ce-doped YAG luminescent ceramic. Wherein the sintering pretreatment comprises the steps of drying, calcining, granulating, sieving and tabletting in sequence.
In the scheme, before roasting, cerium is in a nanometer form and is attached to the surface of yttrium oxide, and is decomposed into cerium oxide after roasting at the temperature of 900-1000 ℃, so that the coating effect is realized.
The technical scheme is that yttrium oxide in a YAG raw material is pretreated by a liquid phase method, cerium oxide is coated on the surface of yttrium oxide powder, a coated yttrium oxide-cerium oxide composite powder material is obtained after drying and roasting, and the powder material is used for preparing the Ce-doped YAG luminescent ceramic by a solid phase method. Cerium in the coated yttrium oxide-cerium oxide composite powder prepared by the method is fully and uniformly contacted with yttrium oxide, so that the reaction efficiency of cerium entering yttrium crystal lattices is improved. Therefore, the problems that the local high lattice distribution of cerium in yttrium causes the quenching of luminous concentration and the low purity of a luminous ceramic phase and a plurality of intermediate phase products exist due to the uneven doping of cerium are solved, and the luminous efficiency of the luminous ceramic is improved. Meanwhile, only a small amount of precipitator is needed, and a large amount of salt solution and acid-base solution are not needed, so that the environment is not polluted and the problem of equipment corrosion is avoided.
The first solution is further described in detail below by means of specific embodiments with reference to the accompanying drawings.
Example one
Referring to fig. 1, the invention discloses a yttrium oxide-cerium oxide composite powder and a method for preparing Ce doped YAG luminescent ceramic using the same, which comprises the following steps:
101. and (4) pretreating yttrium oxide. Weighing 10-50g of yttrium oxide nano powder, putting the yttrium oxide nano powder into 10-200ml of absolute ethyl alcohol for ultrasonic cleaning for 10min, removing the ethyl alcohol by centrifugal separation, and repeatedly cleaning for a plurality of times, usually 3 times; and putting the yttrium oxide nano powder cleaned by the absolute ethyl alcohol into 0.1-0.5M NaOH solution, carrying out ultrasonic treatment for 30-60min, standing for at least 12h, separating and dehydrating by using a centrifugal separator, and then washing by using distilled water until the supernatant is neutral. Filtering the lower layer yttrium oxide nano powder, placing the filtered lower layer yttrium oxide nano powder in a 60 ℃ oven, and baking and drying the filtered lower layer yttrium oxide nano powder for later use.
102. And (4) preparing a suspension. 0.79g of NH are weighed4HCO3Dissolving the solid in a small amount of deionized water, and pouring the solution into a volumetric flask to reach a constant volume of 100ml to obtain 0.1M NH4HCO3Adding 10g of pretreated nanometer yttrium oxide powder into the solution, placing the solution in a high-speed dispersion machine, and mechanically stirring the solution for 30-120min at the rotating speed of 3000 r/min; then ultrasonic dispersion is carried out for 30-120min to obtain suspension. This step corresponds to step (a) in claim 2.
103. And preparing a cerium salt solution. In this example, the ratio of cerium to yttrium is represented by the formula 3(1-x)/2Y2O3+2.5Al2O3+3xCeO2→(Y1-xCex)3Al5O12In this example, x is 0.03. 0.1157g of Ce (NO) were weighed out3)4·6H2Dissolving O in deionized water, diluting to 100ml, and mechanically stirring to obtain Ce (NO)3)·6H2And completely dissolving the O to obtain the cerium salt solution. This step corresponds to step (b) in claim 2.
104. And (4) depositing and coating. And pouring the suspension into a 250ml round-bottom flask, placing the flask in a water tank of a constant-temperature water bath at 60 ℃, mechanically stirring at the rotating speed of 1000r/min, slowly dripping the cerium salt solution into the suspension by using a peristaltic pump at the dripping speed of 10ml/min, continuously stirring for at least 2 hours after dripping is finished, stopping stirring, and aging for 3-12 hours to obtain a mixed solution. And (3) carrying out suction filtration and water washing on the mixed solution for 3-5 times, dehydrating the mixed solution for 3-5 times by using absolute ethyl alcohol, and then placing the dehydrated mixed solution in an oven at 80 ℃ for drying for 8-12h to obtain a precursor of the coated yttrium oxide-cerium oxide composite powder. This step corresponds to step (c) in claim 2.
105. And roasting the precursor to obtain the yttrium oxide-cerium oxide composite powder. And putting the precursor of the coated yttrium oxide-cerium oxide composite powder into a muffle furnace with the temperature of 900 ℃ and the temperature of 1000 ℃ for roasting for 4-6h, wherein the temperature value is 900 ℃ in the embodiment, and the roasting time is 4h, so as to obtain the faint yellow coated yttrium oxide-cerium oxide composite powder. This step corresponds to step (d) in claim 2.
After the yttrium oxide-cerium oxide composite powder is obtained, the Ce-doped YAG luminescent ceramic can be continuously prepared, and the method comprises the following steps:
106. and (5) ball milling and mixing. The molar quantity of Al is obtained according to the molar ratio Ce/Al or Y/Al in the above formula, and the mass of the aluminum compound required is calculated, in this example, 7.5g of Al is weighed2O3Mixing the yttrium oxide-cerium oxide composite powder with Al2O3Adding into a ball milling tank, and adding Al which is 10-20 times of the total powder mass2O3Balls or ZrO2Ball, in this example, 170gAl was added2O3Adding ethanol into the ball, and performing ball milling for 4-8 h.
107. And (4) preparing the ceramic. Ball-milling the mixed powder, drying the powder at constant temperature in vacuum to obtain dry powder, calcining the dry powder to decompose organic components in the powder, and sieving and granulating the decomposed organic components to obtain the high-fluidity luminescent ceramic precursor powder. And (2) filling the luminescent ceramic precursor powder into a mold, pre-pressing under a preset pressure, then putting the pre-pressed sheet into a sintering furnace, and sintering in an inert gas atmosphere or nitrogen hydrogen to obtain the Ce-doped YAG luminescent ceramic.
The second embodiment of the present invention is based on the principle that suspension of yttrium oxide and cerium salt is mixed with H2O2Reacting with ammonia water solution to obtain gel, attaching cerium in a nano form to the surface of yttrium oxide, roasting, and decomposing into cerium oxide to realize a coating effect. In one embodiment of the present invention, the specific steps are as follows:
pretreatment of yttrium oxide: and (3) carrying out ultrasonic cleaning on the yttrium oxide nano powder by absolute ethyl alcohol, ultrasonic cleaning by a low-concentration alkali solution and repeated cleaning by deionized water, and drying for later use. In the ultrasonic cleaning of the low-concentration alkali solution, NaOH solution or other alkali solutions can be used. Although non-pretreated yttria can also be used in the present invention, the inventors have noted that pretreated yttria can achieve better results, both in coating and dispersion.
Preparing a cerium salt solution: the ratio of cerium to yttrium is shown in the chemical formula 3(1-x)/2Y2O3+2.5Al2O3+3xCeO2→(Y1-xCex)3Al5O12Is obtained in which 0<x<0.1. Weighing a certain amount of soluble cerium salt, dissolving in deionized water, and mechanically stirring uniformly to prepare a cerium salt solution with the concentration of 0.01M-2M.
Preparing a suspension: adding a certain amount of pretreated yttrium oxide nano powder into a cerium salt solution, placing the mixture into a high-speed dispersion machine, mechanically stirring the mixture for a period of time at a preset rotating speed, and then ultrasonically dispersing the mixture for a preset time to obtain a suspension. Wherein the order of ultrasonic dispersion and mechanical agitation dispersion may be reversed.
Coating with sol-gel: slowly adding a certain amount of H dropwise into the suspension2O2The solution was stirred continuously using a magnetic stirrer. Then adding H at a certain rate2O2Titrating ammonia water solution with preset concentration in the suspension of the solution, adjusting the pH value, and fully reacting for a period of time to obtain mixed suspension. And (3) filtering and washing the mixed suspension liquid with deionized water for several times, dispersing the washed precipitate with ethanol or ethylene glycol, fully stirring, washing the precipitate for several times again with a vacuum pump, and drying the washed precipitate in a constant-temperature drying box for a certain time. And drying, taking out the precipitate, and grinding in agate grinding to obtain the precursor of the coated yttrium oxide-cerium oxide composite powder.
And roasting the precursor to obtain the yttrium oxide-cerium oxide composite powder. And putting the precursor of the coated yttrium oxide-cerium oxide composite powder into a muffle furnace at a certain temperature for roasting for several hours to obtain the coated yttrium oxide-cerium oxide composite powder.
After the yttrium oxide-cerium oxide composite powder is obtained, the Ce-doped YAG luminescent ceramic can be continuously prepared, and the steps are the same as the first scheme.
In the scheme, before roasting, cerium is attached to the surface of yttrium oxide by nano cerium hydroxide, and is decomposed into cerium oxide after roasting at 400 ℃, so that the coating effect is realized.
The technical scheme is that yttrium oxide in a YAG raw material is pretreated by a liquid phase method, cerium oxide is coated on the surface of yttrium oxide powder, a coated yttrium oxide-cerium oxide composite powder material is obtained after drying and roasting, and the powder material is used for preparing the Ce-doped YAG luminescent ceramic by a solid phase method.
The second solution is further described in detail by the following specific embodiments with reference to the attached drawings.
Example two
Referring to fig. 2, the invention discloses a yttrium oxide-cerium oxide composite powder and a method for preparing Ce doped YAG luminescent ceramic using the same, which comprises the following steps:
201. and (4) pretreating yttrium oxide. Weighing 10-50g of yttrium oxide nano powder, putting the yttrium oxide nano powder into 10-200ml of absolute ethyl alcohol for ultrasonic cleaning for 10min, removing the ethyl alcohol by centrifugal separation, and repeatedly cleaning for a plurality of times, usually 3 times; and putting the yttrium oxide nano powder cleaned by the absolute ethyl alcohol into 0.1-0.5M NaOH solution, carrying out ultrasonic treatment for 30-60min, standing for at least 12h, separating and dehydrating by using a centrifugal separator, and then washing by using distilled water until the supernatant is neutral. Filtering the lower layer yttrium oxide nano powder, placing the filtered lower layer yttrium oxide nano powder in a 60 ℃ oven, and baking and drying the filtered lower layer yttrium oxide nano powder for later use.
202. And preparing a cerium salt solution. In this example, the ratio of cerium to yttrium is represented by the formula 3(1-x)/2Y2O3+2.5Al2O3+3xCeO2→(Y1-xCex)3Al5O12Is obtained in which 0<x<0.1. In this example, x is 0.03. 8.7g of Ce (NO) are weighed3)4·6H2Dissolving the O solid into a small amount of deionized water, diluting to 1000mL, and mechanically stirring uniformly until the Ce (NO) is obtained3)4·6H2The O is completely dissolved.
203. And (4) preparing a suspension. Adding 750g of pretreated yttrium oxide nano powder into a cerium salt solution, placing the mixture into a high-speed dispersion machine, mechanically stirring the mixture for 30-60min at the rotating speed of 3000r/min, and then ultrasonically dispersing the mixture for 30-60min to obtain a suspension.
204. Coating with sol-gel, slowly adding 0.1-1M H dropwise into the suspension2O2The solution was 100ml and stirred continuously using a magnetic stirrer. Then adding into the mixture at a rate of 1-3mL/minH2O2Titrating 0.1-1 mol/concentration ammonia water solution in the suspension of the solution, adjusting the pH value to 8-11, and fully reacting for 2-4h to obtain a mixed suspension. And (3) carrying out suction filtration and washing on the mixed suspension liquid for 3-5 times by using deionized water, dispersing the washed precipitate by using ethanol or ethylene glycol, fully stirring, washing the precipitate for 3-5 times by using a vacuum pump, and drying the washed precipitate in a constant-temperature drying box at 70 ℃ for 12-24 hours. And drying, taking out the precipitate, and grinding in agate grinding to obtain the precursor of the coated yttrium oxide-cerium oxide composite powder.
205. And roasting the precursor to obtain the yttrium oxide-cerium oxide composite powder. And (3) putting the precursor of the coated yttrium oxide-cerium oxide composite powder into a 400 ℃ muffle furnace for roasting for 2-4h to obtain the coated yttrium oxide-cerium oxide composite powder.
After the yttrium oxide-cerium oxide composite powder is obtained, the Ce-doped YAG luminescent ceramic can be continuously prepared, and the method comprises the following steps:
206. and (5) ball milling and mixing. The mass of the desired aluminum compound is calculated by obtaining the molar amount of Al according to the molar ratio Ce/Al or Y/Al in the above formula. In this example, 566g of Al was weighed2O3Mixing the yttrium oxide-cerium oxide composite powder with Al2O3Adding into a ball milling tank, and adding Al which is 10-20 times of the total powder mass2O3Balls or ZrO2 balls, in this example, 13KgAl is added2O3Adding ethanol into the ball, and performing ball milling for 4-8 h.
207. And (4) preparing the ceramic. Ball-milling the mixed powder, drying the powder at constant temperature in vacuum to obtain dry powder, calcining the dry powder to decompose organic components in the powder, and sieving and granulating the decomposed organic components to obtain the high-fluidity luminescent ceramic precursor powder. And (2) filling the luminescent ceramic precursor powder into a mold, pre-pressing under a preset pressure, then putting the pre-pressed sheet into a sintering furnace, and sintering in an inert gas atmosphere or nitrogen hydrogen to obtain the Ce-doped YAG luminescent ceramic.
The Ce-doped YAG luminescent ceramic obtained by the invention can be applied to the fields of illumination and display. For example, it can be applied to an automobile headlamp (particularly, a laser automobile headlamp) as a light emitting element thereof; it can also be applied to a fluorescent color wheel of a projector or a fixed laser fluorescent luminous component. The Ce-doped YAG luminescent ceramic can bear high-power laser irradiation, and greatly improves the luminous efficiency and the luminous brightness.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (7)
1. A preparation method of Ce-doped YAG luminescent ceramic is characterized by comprising the following steps:
(1) preparing yttrium oxide-cerium oxide composite powder: reacting yttrium oxide nano powder with a soluble cerium salt solution in the presence of a precipitator to generate a precursor of coated yttrium oxide-cerium oxide composite powder, and roasting to obtain the coated yttrium oxide-cerium oxide composite powder with cerium oxide coated on the surface of the yttrium oxide nano powder;
(2) preparing Ce-doped YAG luminescent ceramic: mixing the yttrium oxide-cerium oxide composite powder with an aluminum compound, and then carrying out sintering pretreatment and sintering to obtain Ce-doped YAG luminescent ceramic;
the preparation method of the yttrium oxide-cerium oxide composite powder comprises the following steps:
(a) preparing yttrium oxide nano powder suspension: adding the pretreated yttrium oxide nano powder into the solution of the first precipitator, and uniformly dispersing to obtain a uniform suspension;
(b) preparing a soluble cerium salt solution: adding a predetermined amount of soluble cerium salt into water to obtain a soluble cerium salt solution;
(c) deposition and coating: slowly dripping the cerium salt solution into the suspension, stirring and aging to obtain a mixed solution, washing and drying the mixed solution to obtain a precursor of the coated yttrium oxide-cerium oxide composite powder;
(d) roasting a precursor: roasting a precursor of the coated yttrium oxide-cerium oxide composite powder to obtain the coated yttrium oxide-cerium oxide composite powder;
or the step of preparing the yttrium oxide-cerium oxide composite powder comprises the following steps:
(a) preparing a soluble cerium salt solution: adding a predetermined amount of soluble cerium salt into water to obtain a cerium salt solution;
(b) preparing a suspension: adding the pretreated yttrium oxide nano powder into the cerium salt solution to obtain a suspension;
(c) coating with sol-gel: dropwise adding a second precipitator into the suspension, uniformly dispersing to obtain a mixed suspension, washing, drying, and grinding to obtain a precursor of the coated yttrium oxide-cerium oxide composite powder;
(d) roasting a precursor: and roasting the precursor of the coated yttrium oxide-cerium oxide composite powder to obtain the coated yttrium oxide-cerium oxide composite powder.
2. The method according to claim 1, wherein the yttrium oxide nanopowder and the soluble cerium salt are configured in a ratio (1-x)/x of an amount of yttrium substance to an amount of cerium substance, wherein 0< x < 0.1.
3. The method of claim 1, wherein the first precipitating agent is a soluble bicarbonate.
4. The method of claim 1, wherein the first precipitating agent is NH4HCO3The concentration of the solution is 0.01-2 mol/L.
5. The method of claim 1, wherein the second precipitating agent comprises hydrogen peroxide and an aqueous ammonia solution.
6. The preparation method of claim 5, wherein the concentration of the hydrogen peroxide is 0.1-1mol/L, and the concentration of the ammonia water solution is 0.1-1 mol/L.
7. The method according to any one of claims 1 to 6, wherein the aluminum compound comprises at least one of aluminum oxide, aluminum hydroxide, aluminum nitrate, aluminum sulfate, and aluminum carbonate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0889005A1 (en) * | 1997-07-02 | 1999-01-07 | Shin-Etsu Chemical Co., Ltd. | Yttrium oxide-aluminum oxide composite particles and method for the preparation thereof |
| CN101134896A (en) * | 2007-10-16 | 2008-03-05 | 厦门大学 | Method for preparing rare earth doping yttrium aluminium garnet fluorescent powder by oxalic acid non-homogeneous phase deposition |
| CN103058644A (en) * | 2012-12-19 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Method for preparing rare earth doping yttrium aluminum garnet crystalline ceramic through synthesis of rare earth doping Y2O3 nanometer powder |
| CN103755345A (en) * | 2014-01-02 | 2014-04-30 | 甘肃稀土新材料股份有限公司 | Preparation method of granular yttrium cerium oxide solid solution |
| CN103771482A (en) * | 2014-01-09 | 2014-05-07 | 大连交通大学 | Method for preparing high-purity yttrium aluminum garnet nano powder |
Family Cites Families (1)
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|---|---|---|---|---|
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-
2016
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0889005A1 (en) * | 1997-07-02 | 1999-01-07 | Shin-Etsu Chemical Co., Ltd. | Yttrium oxide-aluminum oxide composite particles and method for the preparation thereof |
| CN101134896A (en) * | 2007-10-16 | 2008-03-05 | 厦门大学 | Method for preparing rare earth doping yttrium aluminium garnet fluorescent powder by oxalic acid non-homogeneous phase deposition |
| CN103058644A (en) * | 2012-12-19 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Method for preparing rare earth doping yttrium aluminum garnet crystalline ceramic through synthesis of rare earth doping Y2O3 nanometer powder |
| CN103755345A (en) * | 2014-01-02 | 2014-04-30 | 甘肃稀土新材料股份有限公司 | Preparation method of granular yttrium cerium oxide solid solution |
| CN103771482A (en) * | 2014-01-09 | 2014-05-07 | 大连交通大学 | Method for preparing high-purity yttrium aluminum garnet nano powder |
Non-Patent Citations (1)
| Title |
|---|
| Nanostructured cerium oxide: preparation and properties of weakly-agglomerated powders;Boro Djuričić等;《Journal of the European Ceramic Society》;19991231;第19卷(第11期);第1927页左栏第4段、右栏第4段，第1933页右栏第3段 * |
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