CN100364894C - Alcohol-water compounded solvents coprecipitation method of preparing yttrium aluminium garnet nano-powder - Google Patents
Alcohol-water compounded solvents coprecipitation method of preparing yttrium aluminium garnet nano-powder Download PDFInfo
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- CN100364894C CN100364894C CNB2006100216069A CN200610021606A CN100364894C CN 100364894 C CN100364894 C CN 100364894C CN B2006100216069 A CNB2006100216069 A CN B2006100216069A CN 200610021606 A CN200610021606 A CN 200610021606A CN 100364894 C CN100364894 C CN 100364894C
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Abstract
A preparation method for yttrium aluminum garnet (YAG) nanoparticles by alcohol-water solvent coprecipitation comprises: (1) dissolving yttrium salt and aluminum salt in deionized water to obtain a mixed salt solution with aluminum ion concentration of 0.025~0.2 mol/L, and dissolving ammonium bicarbonate in ethanol-water solvent to obtain a sediment solution with ammonium bicarbonate concentration of 0.4~2 mol/L, (2) titrating the mixed salt solution into the sediment solution under atmospheric pressure at 5-20DEG C and then aging for at least five hours, (3) vacuum-filtering, washing, and drying to YAG precursor, and (4) torrefying the precursor at 900DEG C for 2-3 hours to obtain YAG nanopowders. This method is simple and easy to control conditions, and can prepare single-phase YAG nanopowders stably, which lays a good foundation for industrial production.
Description
Technical field
The invention belongs to the precipitator method and prepare the nano-powder field, particularly a kind of compounded solvents coprecipitation method for preparing nanometer yttrium aluminium garnet powder.
Background technology
(be called for short YAG, chemical formula is Y to yttrium aluminum garnet
3Al
5O
12) nano-powder is the important source material of preparation YAG crystalline ceramics.As everyone knows, the preparation of YAG crystalline ceramics can remedy the shortcoming in the preparation of YAG single crystal, and has and the same excellent optical property of monocrystalline, is the more competitive laser host material that substitutes single crystal.The YAG pottery also has excellent mechanical behavior under high temperature, can be used as high-temperature structural components and is widely used.In addition, doping Eu
3+, Ce
3+And Tb
3+The YAG powder be again good phosphor material powder, be used for cathode tube etc.So the preparation of YAG nano-powder becomes a focus of domestic and international researcher research.
Coprecipitation method is a kind of common method of preparation nanometer yttrium aluminium garnet powder, but concrete technology difference to some extent.Disclosed preparation technology is in the paper that Wang Hongzhi etc. deliver on " Journal of Inorganic Materials " " coprecipitation method prepares nanometer YAG powder " (seeing " Journal of Inorganic Materials " the 16th volume the 4th phase P630-634, July calendar year 2001): Al ((NO
3)
39H
2O, Y (NO
3)
3Wiring solution-forming in proportion, this solution and ammoniacal liquor are added drop-wise to (about 200ml) in the certain solution of pH simultaneously at a slow speed, the while vigorous stirring, obtain precipitation, in this process, keep the pH value of system to keep constant, precipitate through baking oven 100 ℃ of dryings, washing, alcohol and wash, calcine and obtain oxide powder by the rate of titration of regulating ammoniacal liquor.It can be seen from the above, and what this technical scheme adopted is the mode of dripping altogether, in reaction process, need to keep the pH value of system constant by the rate of titration of regulating ammoniacal liquor, thereby complicated operation, be difficult to make the pH value of system constant.Disclosed preparation technology is in the paper that Li Jiang etc. deliver on " silicate journal " " coprecipitation method prepares yttrium aluminum garnet (YAG) nano-powder " (seeing " silicate journal " the 31st volume the 5th phase P490-493, in May, 2003): with the NH of deionized water preparation
4Al (SO
4)
2And Y (NO
3)
3Mixing solutions be raw material, with the NH of deionized water preparation
4HCO
3Solution is precipitation agent, adopts the back titration mode, obtains white precipitate by regulating the pH value and adding polyglycol surfactants, and calcination obtains the YAG powder under different temperature.It can be seen from the above, and this technical scheme not only needs the pH value of conditioned reaction system, and need to add polyglycol surfactants.Disclosed preparation technology is in the paper that Guo Wang, Lu Tiecheng etc. deliver on " functional materials " " coprecipitation method prepares the some influence factors in pure phase yttrium aluminum garnet (YAG) nano-powder " (seeing " functional materials " 2006 the 1st phases (37) volume P66-69): with deionized water preparation Y (NO
3)
3And NH
4Al (SO
4)
2Mixing solutions is with deionized water preparation NH
4HCO
3Precipitant solution under agitation is titrated to NH with mixing solutions
4HCO
3In the solution, titration finishes the back ageing, filters and obtain throw out, obtains presoma with toasting after the throw out washing, and the presoma calcining is obtained the YAG nano-powder.With above-mentioned craft discussion mixing solutions concentration for the influence that generates powder thing phase, precipitation agent concentration is for the influence of powder thing phase, envrionment temperature is for the influence that generates powder thing phase, rate of titration is for the influence that generates pure phase YAG.Experimental result shows: most experiments presoma that sample obtains can not obtain single-phase YAG powder 1100 ℃ of roastings, has only and selects to optimize processing parameter, promptly with 0.015Mol/LY (NO
3)
3With 0.025mol/L NH
4Al (SO
4)
2Be raw material, with 1mol/L NH
4HCO
3Be precipitation agent, under 15 ℃, adopt the titration mode at a slow speed of 4ml/min, the presoma that is obtained could obtain single-phase YAG powder 900 ℃～1100 ℃ roastings.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of alcohol-water compounded solvents coprecipitation method for preparing nanometer yttrium aluminium garnet powder is provided, this kind method not only technology is simple, easy handling, and make the prepared presoma of the mixing salt solution of concentration in a big way and precipitant solution not be higher than 1000 ℃ of roastings in temperature to stablize and obtain the intact single-phase YAG nano-powder of crystallization.
The method of the invention is a kind of improvement to existing coprecipitation method, and main improvements are to replace deionized water as preparation NH with the alcohol-water mixed solution
4HCO
3The solvent of precipitant solution.The processing step of the method for the invention is followed successively by:
(1) preparation reaction soln
By the mol ratio of Y and Al is 3: 5 weighing yttrium salt and aluminium salt, yttrium salt and aluminium salt is dissolved in the deionized water preparation Al
3+Concentration is the mixing salt solution of 0.025mol/L～0.2mol/L, with NH
4HCO
3Be dissolved in the alcohol-water double solvents preparation NH
4HCO
3Concentration is the precipitant solution of 0.4mol/L～2mol/L;
(2) titration and ageing
According to NH
4HCO
3Molar weight and Y
3+And Al
3+The ratio of integral molar quantity is the precipitant solution and the mixing salt solution of measuring step (1) preparation in 9: 1～11: 1, under normal pressure, 5 ℃～20 ℃, with the speed of dripping that is not more than 250ml/h mixing salt solution is titrated in the precipitant solution, constantly stir during titration, at least ageing 5 hours after titration finishes, cause to react completely the precipitation that obtains mixing;
(3) suction filtration and washing
The precipitation solution good to ageing carries out vacuum filtration, obtains white depositions, at first with this throw out washed with de-ionized water, remove the foreign ion of surface adsorption, and then, remove moisture content with the dehydrated alcohol cleaning, prevent that throw out from producing serious reunion by hydrogen bond in oven dry and calcination process;
(4) oven dry and roasting
White depositions oven dry with after the washing obtains the aluminium garnet presoma, and the aluminium garnet presoma normal pressure, 900 ℃～1100 ℃ roastings 2～3 hours, is obtained nanometer yttrium aluminium garnet powder.
Adopt the method for the invention, the volume ratio of ethanol and water is low excessively, and the local proportioning of yttrium and aluminum ion was departed from 3: 5, has intermediate phase to produce, and is difficult to obtain single-phase nanometer yttrium aluminium garnet powder in roasting below 1100 ℃; The volume ratio of ethanol and water is too high then can to cause the ethanol waste, and adds the solubleness that too many ethanol can reduce solute, and the crystallization of dissolved solute is separated out.Test shows, preferred 0.2: 1～1.2: 1 of the volume ratio of ethanol and water.
In the method for the invention, yttrium salt is selected Y (NO for use
3)
3Or YCl
3, aluminium salt is selected NH for use
4Al (SO
4)
2Or Al (NO
3)
3
Beneficial effect of the present invention is:
1, Al
3+Concentration is mixing salt solution, the NH of 0.025mol/L～0.2mol/L
4HCO
3Concentration is the prepared presoma of the precipitant solution of 0.4mol/L～2mol/L, does not have intermediate phase to produce 900 ℃～1100 ℃ roastings, can stablize to obtain single-phase nanometer yttrium aluminium garnet powder, for suitability for industrialized production is laid a good foundation.
2, only be to have changed preparation NH
4HCO
3The solvent of precipitant solution do not need the pH value of conditioned reaction system in precipitin reaction, thereby technology is simple, easy handling.
3, alcohol-water double solvents cost is low, is easy to obtain, and is pollution-free, meets industrial production requirement.
Description of drawings
Fig. 1 is the XRD curve of the presoma roasting obtained product under differing temps among the embodiment 1;
Fig. 2 is the XRD curve of the product of roasting of simultaneous test;
Fig. 3 is the XRD curve of the presoma roasting obtained product under differing temps among the embodiment 2;
Fig. 4 is the XRD curve of the presoma roasting obtained product among embodiment 3, embodiment 4, the embodiment 5.
Embodiment
Embodiment 1
With 0.03mol Y (NO
3)
3With 0.05mol NH
4Al (SO
4)
2Be dissolved in the 600ml deionized water, be mixed with Al
3+Concentration is the 0.083mol/L mixing salt solution, is that 1: 1 alcohol-water double solvents preparation 2000ml concentration is the NH of 0.4mol/L with the volume ratio of ethanol and water
4HCO
3Solution; The speed of dripping with 200ml/h under normal pressure, 15 ℃ is titrated to 2000ml NH with the mixing salt solution of being prepared
4HCO
3In the solution, titration process constantly stirs.After titration finishes, normal pressure, 15 ℃ of following ageings 8 hours; The precipitation solution good to ageing carries out vacuum filtration, obtains the milky white precipitate thing, then with deionized water with sediment undergoes washing 3 times, remove foreign ion, clean 2 times with dehydrated alcohol again, remove moisture; White depositions after the washing is put into loft drier, obtained the YAG presoma in 24 hours in normal pressure, 90 ℃ of dryings, the YAG presoma is divided into three parts, respectively at 900 ℃, 1000 ℃, 1100 ℃ roastings 2 hours, and the products therefrom X-ray diffractometer (XRD, the D/max2rA type changes target, parameter is Cu K α radiation, 40kV * 110mA) detect is single-phase YAG nano-powder, and its XRD curve is seen Fig. 1.
Simultaneous test: the used starting material of simultaneous test are identical with embodiment 1, and processing step is identical with embodiment 1 with processing parameter, different only be to be that solvent preparation 2000ml concentration is the NH of 0.4mol/L with deionized water
4HCO
3Solution.The product of roasting of simultaneous test X-ray diffractometer (XRD, the D/max2rA type changes target, and parameter is Cu K α radiation, 40kV * 110mA) detect, its XRD curve is seen Fig. 2, as can be seen from Figure 2, product of roasting is not single-phase YAG nano-powder, has produced intermediate phase Y
2O
3, YAM (Y
4Al
2O
9).
Embodiment 2
With 0.072mol Y (NO
3)
3With 0.12mol Al ((NO
3)
3Be dissolved in the 600ml deionized water, be mixed with Al
3+Concentration is the 0.2mol/L mixing salt solution, is that 0.2: 1 alcohol-water double solvents preparation 1200ml concentration is the NH of 1.5mol/L with the volume ratio of ethanol and water
4HCO
3Solution; The speed of dripping with 180ml/h under normal pressure, 15 ℃ is titrated to 1200ml NH with the mixing salt solution of being prepared
4HCO
3In the solution, titration process constantly stirs.After titration finishes, normal pressure, 15 ℃ of following ageings 10 hours; The precipitation solution good to ageing carries out vacuum filtration, obtains white depositions, then with deionized water with sediment undergoes washing 3 times, remove foreign ion, clean 2 times with dehydrated alcohol again, remove moisture; White depositions after the washing is put into loft drier, obtained the YAG presoma in 24 hours in normal pressure, 90 ℃ of dryings, the YAG presoma is divided into three parts, respectively at 900 ℃, 1000 ℃, 1100 ℃ roastings 3 hours, and the products therefrom X-ray diffractometer (XRD, the D/max2rA type changes target, parameter is Cu K α radiation, 40kV * 110mA) detect is single-phase YAG nano-powder, and its XRD curve is seen Fig. 3.
Embodiment 3
With 0.03mol YCl
3With 0.05mol NH
4Al (SO
4)
2Be dissolved in the 2000ml deionized water, be mixed with Al
3+Concentration is the 0.025mol/L mixing salt solution, is that 0.5: 1 alcohol-water double solvents preparation 800ml concentration is the NH of 1mol/L with the volume ratio of ethanol and water
4HCO
3Solution; The speed of dripping with 250ml/h under normal pressure, 10 ℃ is titrated to 800ml NH with the mixing salt solution of being prepared
4HCO
3In the solution, titration process constantly stirs.After titration finishes, normal pressure, 10 ℃ of following ageings 5 hours; The precipitation solution good to ageing carries out vacuum filtration, obtains white depositions, then with deionized water with sediment undergoes washing 3 times, remove foreign ion, clean 2 times with dehydrated alcohol again, remove moisture; White depositions after the washing is put into loft drier, obtained the YAG presoma in 24 hours in normal pressure, 90 ℃ of dryings, with the YAG presoma in 1000 ℃ of roastings 2 hours, products therefrom X-ray diffractometer (XRD, the D/max2rA type changes target, and parameter is Cu K α radiation, 40kV * 110mA) detect, be single-phase YAG nano-powder, its XRD curve is seen Fig. 4.
Embodiment 4
With 0.03mol Y (NO
3)
3With 0.05mol NH
4Al (SO
4)
2Be dissolved in the 600ml deionized water, be mixed with Al
3+Concentration is the 0.083mol/L mixing salt solution, is that 1.2: 1 alcohol-water double solvents preparation 1500ml concentration is the NH of 0.6mol/L with the volume ratio of ethanol and water
4HCO
3Solution; The speed of dripping with 200ml/h under normal pressure, 20 ℃ is titrated to 1500ml NH with the mixing salt solution of being prepared
4HCO
3In the solution, titration process constantly stirs.After titration finishes, normal pressure, 20 ℃ of following ageings 5 hours; The precipitation solution good to ageing carries out vacuum filtration, obtains white depositions, then with deionized water with sediment undergoes washing 3 times, remove foreign ion, clean 2 times with dehydrated alcohol again, remove moisture content; White depositions after the washing is put into loft drier, obtained the YAG presoma in 24 hours in normal pressure, 90 ℃ of dryings, with the YAG presoma in 1000 ℃ of roastings 2 hours, products therefrom X-ray diffractometer (XRD, the D/max2rA type changes target, and parameter is Cu K α radiation, 40kV * 110mA) detect, be single-phase YAG nano-powder, its XRD curve is seen Fig. 4.
Embodiment 5
With 0.03mol Y (NO
3)
3With 0.05mol NH
4Al (SO
4)
2Be dissolved in the 600ml deionized water, be mixed with Al
3+Concentration is the 0.083mol/L mixing salt solution, is that 0.2: 1 alcohol-water double solvents preparation 1500ml concentration is the NH of 0.6mol/L with the volume ratio of ethanol and water
4HCO
3Solution; The speed of dripping with 200ml/h under normal pressure, 5 ℃ is titrated to 1500ml NH with the mixing salt solution of being prepared
4HCO
3In the solution, titration process constantly stirs.After titration finishes, normal pressure, 5 ℃ of following ageings 5 hours; The precipitation solution good to ageing carries out vacuum filtration, obtains white depositions, then with deionized water with sediment undergoes washing 3 times, remove foreign ion, clean 2 times with dehydrated alcohol again, remove moisture content; White depositions after the washing is put into loft drier, obtained the YAG presoma in 24 hours in normal pressure, 90 ℃ of dryings, with the YAG presoma in 1000 ℃ of roastings 2 hours, products therefrom X-ray diffractometer (XRD, the D/max2rA type changes target, and parameter is Cu K α radiation, 40kV * 110mA) detect, be single-phase YAG nano-powder, its XRD curve is seen Fig. 4.
Claims (2)
1. alcohol-water compounded solvents coprecipitation method for preparing nanometer yttrium aluminium garnet powder is characterized in that the processing step of this method is followed successively by:
(1) preparation reaction soln
By the mol ratio of Y and Al is 3: 5 weighing yttrium salt and aluminium salt, yttrium salt and aluminium salt is dissolved in the deionized water preparation Al
3+Concentration is the mixing salt solution of 0.025mol/L～0.2mol/L, with NH
4HCO
3Be dissolved in the alcohol-water double solvents preparation NH
4HCO
3Concentration is the precipitant solution of 0.4mol/L～2mol/L,
Described alcohol-water double solvents, the volume ratio of ethanol and water are 0.2: 1～1.2: 1;
(2) titration and ageing
According to NH
4HCO
3Molar weight and Y
3+And Al
3+The ratio of integral molar quantity is the precipitant solution and the mixing salt solution of measuring step (1) preparation in 9: 1～11: 1, under normal pressure, 5 ℃～20 ℃, with the speed of dripping that is not more than 250ml/h mixing salt solution is titrated in the precipitant solution, constantly stirs during titration, ageing 5 hours at least after titration finishes;
(3) suction filtration and washing
The precipitation solution good to ageing carries out vacuum filtration, obtains white depositions, and this throw out is cleaned with dehydrated alcohol after with washed with de-ionized water again;
(4) oven dry and roasting
White depositions oven dry with after the washing obtains the aluminium garnet presoma, and the aluminium garnet presoma normal pressure, 900 ℃～1100 ℃ roastings 2～3 hours, is obtained nanometer yttrium aluminium garnet powder.
2. the alcohol-water compounded solvents coprecipitation method of preparation nanometer yttrium aluminium garnet powder according to claim 1 is characterized in that described yttrium salt is Y (NO
3)
3Or YCl
3, described aluminium salt is NH
4Al (SO
4)
2Or Al (NO
3)
3
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| CN101985398A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for preparing transparent polycrystalline Re:YAG ceramic |
| CN101905481B (en) * | 2010-07-08 | 2012-11-14 | 山东大学 | Porous ceramic negative pressure slip casting device and method for preparing ceramic blank |
| CN102391871A (en) * | 2011-10-25 | 2012-03-28 | 湘潭大学 | Preparation method of nano yttrium aluminum garnet fluorescent powder |
| CN103771482B (en) * | 2014-01-09 | 2016-01-27 | 大连交通大学 | A kind of preparation method of high-purity nanometer yttrium aluminium garnet powder |
| CN104229857B (en) * | 2014-08-14 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of the YAG crystallite of morphology controllable |
| CN104445341B (en) * | 2014-11-24 | 2016-09-14 | 广东工业大学 | A kind of preparation method of the nanometer yttrium aluminium garnet powder of pure YAG phase |
| CN114181702B (en) * | 2021-12-24 | 2024-01-05 | 江阴加华新材料资源有限公司 | Preparation method of cerium-doped yttrium aluminum garnet fluorescent powder |
| CN115159963A (en) * | 2022-03-28 | 2022-10-11 | 武汉理工大学 | Y-ZrO 2 /Al 2 O 3 Preparation method of system composite powder |
| CN115142115B (en) * | 2022-07-13 | 2024-04-16 | 罗首其 | Powder coprecipitation preparation method special for magnesia-alumina spinel large single crystal |
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| US5037577A (en) * | 1988-07-30 | 1991-08-06 | Sony Corporation | Method for producing yttrium-aluminum-garnet fine particles and yttrium-aluminum-garnet base phosphor fine particles |
| CN1114502A (en) * | 1993-08-11 | 1996-01-03 | 住友化学工业株式会社 | Composite metal oxide powder and process for producing the same |
| CN1442364A (en) * | 2003-04-15 | 2003-09-17 | 山东大学 | Preparation method of spherical agglomeration less yttrium aluminium garnet nano micropowder |
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2006
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037577A (en) * | 1988-07-30 | 1991-08-06 | Sony Corporation | Method for producing yttrium-aluminum-garnet fine particles and yttrium-aluminum-garnet base phosphor fine particles |
| CN1114502A (en) * | 1993-08-11 | 1996-01-03 | 住友化学工业株式会社 | Composite metal oxide powder and process for producing the same |
| CN1442364A (en) * | 2003-04-15 | 2003-09-17 | 山东大学 | Preparation method of spherical agglomeration less yttrium aluminium garnet nano micropowder |
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