CN101225301B - Method for preparing nano hexa-aluminate based luminescent material - Google Patents
Method for preparing nano hexa-aluminate based luminescent material Download PDFInfo
- Publication number
- CN101225301B CN101225301B CN2008100172924A CN200810017292A CN101225301B CN 101225301 B CN101225301 B CN 101225301B CN 2008100172924 A CN2008100172924 A CN 2008100172924A CN 200810017292 A CN200810017292 A CN 200810017292A CN 101225301 B CN101225301 B CN 101225301B
- Authority
- CN
- China
- Prior art keywords
- purity
- oil
- metal salt
- salt solution
- precursor powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention provides a preparation method for a nanometer hexaaluminate luminescent material, which comprises following steps: combining inverse microemulsion method and precipitation method to obtain nanometer precursor powder through controlling the volume ratio of solution and oil phase in microemulsion; calcining the precursor powder in reducing atmosphere at 1200 to 1350 DEG C to obtain the spherical nanometer luminescent material. The preparation method for the nanometer hexaaluminate luminescent material has the advantages of cheap and available raw material, environmental friendliness, avoidance of pollution, low calcination temperature, even mixing for easy material reduction, low concentration of doped coactivator, and wider rang and easier preparation of the solution of spherical product compared with oil.
Description
Technical field
The invention belongs to inorganic embedded photoluminescent material technical field, relate to a kind of employing Mn, have the preparation method of the hexa-aluminate based nano luminescent material of spherical pattern as activator.
Background technology
Nano-phosphor has the quantum yield height for the micrometer fluorescent powder of prior art for preparing, fluorescence lifetime changes, and therefore characteristics such as spectrum frequency displacement have huge using value in the photoelectric device field.Particularly for plasma display (plasma display panels, PDP) and Field Emission Display (Field emission display panels, FED) two kinds of technique of display, the penetration depth of both driving sources---vacuum-ultraviolet light and Low-voltage Electronic is more shallow, but use nano-phosphor more efficient use excitation energy, save the usage quantity of luminescent material, and can realize reducing of pixel, thus the sharpness of raising display device.In addition, the granule-morphology of nano luminescent material also has material impact for luminescent properties: compare with the random pattern particle that ordinary method obtains, luminescent material with spherical pattern, the ratio minimum that exciting light loses in particle surface generation diffuse-reflectance, therefore under the situation that the activator doping content equates, particle diameter is similar, the brightness of the luminescent material of spherical pattern will be higher than the particle of other pattern.
BaAl
12O
19: Mn and BaMgAl
10O
17: Mn is two kinds of commercial hexa-aluminate based luminescent materials, has obtained using widely on PDP.High temperature solid-state method is all adopted in both commercial productions at present, often needs 1500-1600 ℃ high temperature, and not only the cost high energy consumption is big, and the fluorescent powder grain out-of-shape that generates, even has serious sintering phenomenon.Though can particle be pulverized by ball milling, but mechanical milling process tends to cause particle surface to be damaged, but mechanical milling process tends to cause particle surface to be damaged, producing lattice imperfection or unbodied not luminescent layer is inert layer, thereby reduce the luminous efficiency of material, and only can be crushed to micron order.Though be the synthesis temperature of reduction high temperature solid-state method, the method that adds fusing assistant adopted, as BaF
2Or H
3BO
3Deng, but the use of fusing assistant increases the weight of the agglomerating degree easily, and introduce defective such as colour center.
Prior art also has the reverse microemulsion process of employing to prepare six barium aluminate nano-powders, and with its solid support material (Nature as the catalyticcombustion material, 2000,403:65-67.), but this technology uses metal alkoxide as reaction raw materials, price is high, thereby is not suitable for preparing the bigger luminescent material BaAl of usage quantity
12O
19: Mn and BaMgAl
10O
17: Mn.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano hexa-aluminate based luminescent material can obtain having the nano luminescent material of spherical pattern, and required calcining temperature is low, raw material is cheap and easy to get.
The technical solution adopted in the present invention is that a kind of preparation method of nano hexa-aluminate based luminescent material comprises the steps:
A) with volume ratio be 40%～55% oil, 20%～35% tensio-active agent, 5%～15% cosurfactant, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, to add 5%～25% concentration then therein gradually be the metal salt solution of 0.05～0.5M, be 1～3 with the nitre acid for adjusting pH value, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 40%～55% oil, 20%～35% tensio-active agent, 5%～15% cosurfactant, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, add 5%～25% concentration then therein gradually and be 0.5～0.75M sal volatile, to regulate the pH value with ammoniacal liquor be 9～11, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
B) will go up the reverse micro emulsion RM1 that goes on foot the oil/metal salt solution that obtains, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, reacted 0.5～3 hour, ageing 4～36 hours, centrifugal then or vacuum-drying separation obtains precursor powder;
C) will go up the precursor powder that obtains of step respectively with acetone, alcohol and distilled water wash;
D) precursor powder that will go up then after the step handles is soaked in a small amount of alcohol or the distilled water, disperses under stirring or ultra-sonic oscillation, dries in baking oven again, and temperature of oven is controlled at 80 ℃～120 ℃;
E) add dispersion agent in the precursor powder after last step processing, press mass ratio control, wherein dispersion agent is 1%～15%, precursor powder is 85%～99%, behind the uniform mixing under air atmosphere with 300 ℃～800 ℃ pre-treatment 10～40 minutes, calcined in reducing atmosphere then 2～6 hours, calcining temperature is controlled at 1200 ℃～1400 ℃, promptly obtains the spheric nano hexa-aluminate based luminescent material.
As improvement of the technical scheme, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mn (the CH of O and purity 99.0%
3COO)
24H
2O is according to chemical formula BaAl
11.9O
19: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.05M, and be 1 with the nitre acid for adjusting pH value.
Perhaps, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Be mixed with the metal salt solution that concentration is 0.14M, and be 2 with the nitre acid for adjusting pH value.
Perhaps, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O and purity 99.0%
3COO)
2.4H
2O is according to chemical formula BaMg
0.9Al
10O
17: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.5M, and be 3 with the nitre acid for adjusting pH value.
Perhaps, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Mg
0.9Al
10O
17: 0.1Mn
2+, 0.005Eu
2+Be mixed with the metal salt solution that concentration is 0.3M, and be 3 with the nitre acid for adjusting pH value.
As further improvement in the technical proposal,
Cosurfactant is a n-hexyl alcohol.
Oil is hexanaphthene or normal hexane.
Dispersion agent is ammonium chloride or volatile salt.
The invention has the advantages that:
1) can obtain having the nano luminescent material of spherical pattern;
2) raw material is cheap and easy to get, and environmentally friendly, is difficult for polluting;
3) needed calcining temperature is low, than low 200～300 ℃ of high temperature solid-state method;
4) uniform mixing of easy realization response raw material can be realized the doping of the coactivator of lower concentration;
5) it is big with the scope of oil phase ratio to obtain the solution of spherical products, preparation easily;
6) oil, cosurfactant, the tensio-active agent of isolating in the surplus liquid behind the precursor powder can utilize three's boiling point difference to give Separation and Recovery, reuses.
Description of drawings
Fig. 1 is a nano hexa-aluminate based luminescent material preparation method process flow sheet of the present invention;
Fig. 2 is the BaAl that the inventive method prepares
11.9O
19: 0.1Mn
2+X-ray diffraction XRD figure after the differing temps calcining;
Fig. 3 is the nanometer BaAl that the inventive method prepares
12-xO
19: xMn
2+The emmission spectrum of series of samples under 147nm excites;
Fig. 4 is the Ba that the inventive method prepares
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+With BaAl
11.9O
19: 0.1Mn
2+The emmission spectrum of nano luminescent material under 147nm excites;
Fig. 5 is the BaAl that the inventive method prepares
11.9O
19: 0.1Mn
2+Emmission spectrum under 254nm excites;
Fig. 6 is the Ba that the inventive method prepares
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Emmission spectrum under 254nm excites;
Fig. 7 is the BaAl that the inventive method prepares
11.9O
19: 0.1Mn
2+With Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Excite CIE chromaticity coordinates figure down at 254nm.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples.
Method of the present invention is the method that adopts reverse micro emulsion to combine with the precipitator method, preparation spheric nano hexa-aluminate based luminescent material.For preparation spheric BaAl
12-xO
19: x Mn
2+With spheric BaMgAl
10-xO
17: x Mn
2+Nano hexa-aluminate based luminescent material, Mn
2+Doping be between x=0.07～0.5.
Eu
2+Be a kind of energy sensitization Mn
2+Luminous effective co-dopant ions, but the excessive words of doping then Eu can occur
2+Blue light feature emission, have a strong impact on the purity of color of material.Particularly for spheric nanometer Ba
1-yAl
12-xO
19: x Mn
2+, yEu
2+And Ba
1-yMg
1-xAl
10O
17: xMn
2+, y Eu
2+, Eu
2+Doping need be controlled in the y=0.005, low like this codoped concentration will make oxide raw material uniform mixing difficulty very big for high temperature solid-state method.And for micro emulsion method-precipitator method process combined that the present invention adopts, then can realize the uniform mixing of raw material very easily at molecular level.
As shown in Figure 1, the preparation method of nano hexa-aluminate based luminescent material of the present invention carries out as follows:
A) prepare the reverse micro emulsion RM1 of oil/metal salt solution and the reverse micro emulsion RM2 of oil/sal volatile respectively
Wherein, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mn (the CH of O and purity 99.0%
3COO)
24H
2O is according to chemical formula BaAl
11.9O
19: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.05M, and be 1 with the nitre acid for adjusting pH value.
Then by the volatile salt preparation of purity 99.0%, concentration is 0.5M to sal volatile, and regulating the pH value with ammoniacal liquor is 9.
Perhaps, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Be mixed with the metal salt solution that concentration is 0.14M, and be 2 with the nitre acid for adjusting pH value.
Then by the volatile salt preparation of purity 99.0%, concentration is 0.625M to sal volatile, and regulating the pH value with ammoniacal liquor is 10.
Perhaps, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O and purity 99.0%
3COO)
24H
2O is according to chemical formula BaMg
0.9Al
10O
17: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.5M, and be 2 with the nitre acid for adjusting pH value.
Then by the volatile salt preparation of purity 99.0%, concentration is 0.75M to sal volatile, and regulating the pH value with ammoniacal liquor is 11.
Perhaps, metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Mg
0.9Al
10O
17: 0.1Mn
2+, 0.005Eu
2+Be mixed with the metal salt solution that concentration is 0.3M, and be 2 with the nitre acid for adjusting pH value.
Then by the volatile salt preparation of purity 99.0%, concentration is 0.7M to sal volatile, regulates pH value 11 with ammoniacal liquor.
With volume ratio is 40%～55% oil, 20%～35% tensio-active agent, 5%～15% cosurfactant, under the condition of stirring or ultra-sonic oscillation, mix, add 5%～25% metal salt solution then therein gradually, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 40%～55% oil, 20%～35% tensio-active agent, 5%～15% cosurfactant, under the condition of stirring or ultra-sonic oscillation, mix, add 5%～25% sal volatile then therein gradually, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
B) the reverse micro emulsion RM1 of oil/metal salt solution that step a is obtained, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, reacted 0.5～3 hour, ageing 4～36 hours, centrifugal then or vacuum-drying separation obtains precursor powder;
C) will go up the precursor powder that obtains of step respectively with acetone, alcohol and distilled water wash;
D) precursor powder that will go up after the step handles is soaked in a small amount of alcohol or the distilled water, disperses under stirring or ultra-sonic oscillation, dries in baking oven, and temperature of oven is controlled at 80 ℃～120 ℃;
E) add dispersion agent ammonium chloride or volatile salt in the precursor powder after last step processing, press mass ratio control, wherein dispersion agent is 1%～15%, precursor powder is 85%～99%, behind the uniform mixing under air atmosphere with 300 ℃～800 ℃ pre-treatment 10～40 minutes, calcined in reducing atmosphere then 2～6 hours, calcining temperature is controlled at 1200 ℃～1400 ℃, promptly obtains the spheric nano hexa-aluminate based luminescent material.
Provide preparation spheric nanometer BaAl below respectively
12-xO
19: xMn
2+With BaMg
1-xAl
10O
17: xMn
2+Embodiment:
Embodiment 1
BaAl
12O
19: Mn
2+The preparation of nano luminescent material:
Metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mn (the CH of O and purity 99.0%
3COO)
2.4H
2O is according to chemical formula BaAl
11.9O
19: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.05M, and be 1 with the nitre acid for adjusting pH value.Preparation volatile salt concentration is the solution of 0.625M, and to regulate the pH value with ammoniacal liquor be 9.
With volume ratio is 40% hexanaphthene, 20% OP10,15% n-hexyl alcohol, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 25% concentration then therein gradually is that 0.05M, pH value are 1 metal salt solution, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 40% hexanaphthene, 20% OP10,15% n-hexyl alcohol, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 25% concentration then therein gradually is that 0.5M, pH value are 9 sal volatile, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
With the reverse micro emulsion RM1 of oil/metal salt solution, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, hybrid reaction 0.5 hour, water-oil ratio are 1/3.Ageing after 4 hours centrifugation go out precursor powder.Then with isolated precursor powder respectively with acetone, alcohol, distilled water wash.Precursor powder after the washing is soaked in a small amount of alcohol or the distilled water, under stirring or ultra-sonic oscillation, disperses, in 80 ℃ baking oven, dry then.With mass ratio be after the oven dry of 1% ammonium chloride and 99% the precursor powder mixed grinding evenly the back under air atmosphere with 800 ℃ of pre-treatment 10 minutes, then at reducing atmosphere 5%H
2/ 95%N
2In with 1400 ℃ of calcinings 2 hours, take out behind the furnace cooling and carefully grind, promptly get spheric nanometer BaAl
11.9O
19: 0.1Mn
2+
BaAl
12O
19: Mn
2+, Eu
2+The preparation of nano luminescent material:
The metal salt solution of present embodiment is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Be mixed with the metal salt solution that concentration is 0.14M, and be 2 with the nitre acid for adjusting pH value.Preparation volatile salt concentration is the solution of 0.625M, and to regulate the pH value with ammoniacal liquor be 10.
With volume ratio is 55% normal hexane, 35% triton X-100,5% n-hexyl alcohol, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 5% concentration then therein gradually is that 0.14M, pH value are 2 metal salt solution, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 55% normal hexane, 35% triton X-100,5% n-hexyl alcohol, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 5% concentration then therein gradually is that 0.625M, pH value are 10 sal volatile, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
With the reverse micro emulsion RM1 of oil/metal salt solution, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, hybrid reaction 3 hours, water-oil ratio are 1/3.Ageing after 36 hours centrifugation go out precursor powder.Then with washing with acetone once with isolated precursor powder, the alcohol washed twice, distilled water wash is once.Precursor powder after the washing is soaked in a small amount of alcohol or the distilled water, under stirring or ultra-sonic oscillation, disperses, in 120 ℃ baking oven, dry then.With mass ratio be after the oven dry of 15% volatile salt and 85% the precursor powder mixed grinding evenly the back under air atmosphere with 500 ℃ of pre-treatment 20 minutes, at reducing atmosphere 5%H
2/ 95%N
2In with 1200 ℃ of calcinings 6 hours, take out behind the furnace cooling and carefully grind, promptly get spheric nanometer Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+
BaMgAl
10O
17: Mn
2+The preparation of nano luminescent material:
Metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O and purity 99.0%
3COO)
24H
2O is according to chemical formula BaMg
0.9Al
10O
17: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.5M, and be 3 with the nitre acid for adjusting pH value; Preparation volatile salt concentration is the solution of 0.75M, and to regulate the pH value with ammoniacal liquor be 11.
With volume ratio is 50% hexanaphthene, 30% OP10,10% n-hexyl alcohol, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 10% concentration then therein gradually is that 0.5M, pH value are 3 metal salt solution, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 50% hexanaphthene, 30% OP10,10% n-hexyl alcohol, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 10% concentration then therein gradually is that 0.75M, pH value are 11 sal volatile, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
With the reverse micro emulsion RM1 of oil/metal salt solution, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, hybrid reaction 2.5 hours, water-oil ratio are 1/3.Ageing after 30 hours centrifugation go out precursor powder.Then with washing with acetone once with isolated precursor powder, the alcohol washed twice, distilled water wash is once.Precursor powder after the washing is soaked in a small amount of alcohol or the distilled water, under stirring or ultra-sonic oscillation, disperses, in 110 ℃ baking oven, dry then.With mass ratio be after the oven dry of 5% ammonium chloride and 95% the precursor powder mixed grinding evenly the back under air atmosphere with 300 ℃ of pre-treatment 40 minutes, at reducing atmosphere 5%H
2/ 95%N
2In with 1300 ℃ of calcinings 4 hours, take out behind the furnace cooling and carefully grind, promptly get spheric nanometer BaMg
0.9Al
10O
17: 0.1Mn
2+
BaMgAl
10O
17: Mn
2+, Eu
2+The preparation of nano luminescent material:
Metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Mg
0.9Al
10O
17: 0.1Mn
2+, 0.005Eu
2+Be mixed with the metal salt solution that concentration is 0.3M, and be 3 with the nitre acid for adjusting pH value; Preparation volatile salt concentration is the solution of 0.7M, and to regulate the pH value with ammoniacal liquor be 11.
With volume ratio is 45% normal hexane, 25% triton X-100,14% ammonium chloride, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 16% concentration then therein gradually is that 0.3M, pH value are 3 metal salt solution, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 45% normal hexane, 25% triton X-100,14% ammonium chloride, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, adding 16% concentration then therein gradually is that 0.7M, pH value are 11 sal volatile, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
With the reverse micro emulsion RM1 of oil/metal salt solution, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, hybrid reaction 4 hours, water-oil ratio are 1/3.Ageing after 20 hours centrifugation go out precursor powder.Then with washing with acetone once with isolated precursor powder, the alcohol washed twice, distilled water wash is once.Precursor powder after the washing is soaked in a small amount of alcohol or the distilled water, under stirring or ultra-sonic oscillation, disperses, in 90 ℃ baking oven, dry then.With mass ratio be after the oven dry of 12% volatile salt and 88% the precursor powder mixed grinding evenly the back under air atmosphere with 400 ℃ of pre-treatment 30 minutes, at reducing atmosphere 5%H
2/ 95%N
2In with 1350 ℃ the calcining 3.5 hours, take out behind the furnace cooling, promptly get spheric nanometer Ba
0.995Mg
0.9Al
10O
17: 0.1Mn
2+, 0.005Eu
2+
Use the D/max-2400 type x-ray powder diffraction instrument of Japan (Rigaku) company of science to carry out test analysis mutually to the thing of the above-mentioned spheric nano hexa-aluminate based luminescent material that makes; Luminescent properties with FLS920T vacuum ultraviolet (VUV)-visible test system and test spheric nano hexa-aluminate based luminescent material.
As shown in Figure 2, the result by XRD test as can be known, the BaAl that obtains with embodiment 1
11.9O
19: 0.1Mn
2+Be example, substantially free of impurities existed mutually when calcining temperature was 1200 ℃; Just can obtain well-crystallized's product during to 1300 ℃.It is synthetic temperature required to this shows that used synthetic method of the present invention has effectively reduced.
Vacuum ultraviolet (VUV)-UV luminescent characteristics test:
Fig. 3 is the nanometer BaAl with synthetic method preparation of the present invention
12-xO
19: x Mn
2+The emmission spectrum of series of samples under 147nm excites.As seen from the figure, quencher takes place when doping x=0.2, promptly optimum doping concentration is x=0.2.
Fig. 4 is the Ba of synthetic method preparation of the present invention
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+With BaAl
11.9O
19: 0.1Mn
2+The emmission spectrum of nano luminescent material under 147nm excites, as seen from the figure, codoped Eu
2+The emissive porwer of sample be much higher than the Eu that do not mix
2+Sample, its emissive porwer has improved 65% approximately, and does not observe Eu in the emmission spectrum
2+The emission of blue feature, this shows, adopt the sample raw material of this method preparation to mix, respond well.
Fig. 5 is spheric nanometer BaAl
11.9O
19: 0.1Mn
2+Emmission spectrum under 254nm excites.
Fig. 6 is spheric nanometer Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Emmission spectrum under 254nm excites.
By Fig. 5 and Fig. 6 as seen, spheric nanometer BaAl
11.9O
19: 0.1Mn
2+With spheric nanometer Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+All has abundant emission band in both spectrum.
As shown in Figure 7, the BaAl for preparing of the inventive method
11.9O
19: 0.1Mn
2+With Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Excite CIE chromaticity coordinates figure down at 254nm.
Spheric nanometer BaAl
11.9O
19: 0.1Mn
2+With spheric nanometer Ba
0.995Al
11.9O
19: 0.1Mn
2+, 0.005Eu
2+Emission band in both spectrum is after match, and the chromaticity coordinates that obtains both all is arranged in the white light area of CIE chromaticity diagram, and this is significant for illuminating device.
Claims (1)
1. the preparation method of a nano hexa-aluminate based luminescent material is characterized in that, this method comprises the steps:
A) with volume ratio be 40%～55% oil, 20%～35% tensio-active agent, 5%～15% cosurfactant, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, to add 5%～25% concentration then therein gradually be the metal salt solution of 0.05～0.5M, be 1～3 with the nitre acid for adjusting pH value, the maintenance system is vitreous state, makes the reverse micro emulsion RM1 of oil/metal salt solution;
With volume ratio is 40%～55% oil, 20%～35% tensio-active agent, 5%～15% cosurfactant, under the condition of stirring or ultra-sonic oscillation, mix, dissolve, add 5%～25% concentration then therein gradually and be 0.5～0.75M sal volatile, to regulate the pH value with ammoniacal liquor be 9～11, the maintenance system is vitreous state, makes the reverse micro emulsion RM2 of oil/sal volatile;
B) will go up the reverse micro emulsion RM1 that goes on foot the oil/metal salt solution that obtains, slowly add among the reverse micro emulsion RM2 of oil/sal volatile, under stirring or sonic oscillation condition, reacted 0.5～3 hour, ageing 4～36 hours, centrifugal then or vacuum-drying separation obtains precursor powder;
C) will go up the precursor powder that obtains of step respectively with acetone, alcohol and distilled water wash;
D) precursor powder that will go up then after the step handles is soaked in a small amount of alcohol or the distilled water, disperses under stirring or ultra-sonic oscillation, dries in baking oven again, and temperature of oven is controlled at 80 ℃～120 ℃;
E) add dispersion agent in the precursor powder after last step processing, press mass ratio control, wherein dispersion agent is 1%～15%, precursor powder is 85%～99%, behind the uniform mixing under air atmosphere with 300 ℃～800 ℃ pre-treatment 10～40 minutes, calcined in reducing atmosphere then 2～6 hours, calcining temperature is controlled at 1200 ℃～1400 ℃, promptly obtains the spheric nano hexa-aluminate based luminescent material; Described dispersion agent is ammonium chloride or volatile salt;
In the step a), described metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O and purity 99.0%
3COO)
24H
2O is according to chemical formula BaMg
0.9Al
10O
17: 0.1Mn
2+Be mixed with the metal salt solution that concentration is 0.5M, and be 3 with the nitre acid for adjusting pH value;
Or described metal salt solution is by the Ba (NO of purity 99.5%
3)
2, purity 99.0% Al (NO
3)
39H
2Mg (the NO of O, purity 99.5%
3)
26H
2Mn (the CH of O, purity 99.0%
3COO)
24H
2O and the Eu that is dissolved in the purity 99.99% in the concentrated nitric acid
2O
3, according to chemical formula Ba
0.995Mg
0.9Al
10O17:0.1Mn
2+, 0.005Eu2+ is mixed with the metal salt solution that concentration is 0.3M, and is 3 with the nitre acid for adjusting pH value;
Described tensio-active agent is OP10 or triton X-100;
Described cosurfactant is a n-hexyl alcohol;
Described oil is hexanaphthene or normal hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100172924A CN101225301B (en) | 2008-01-15 | 2008-01-15 | Method for preparing nano hexa-aluminate based luminescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100172924A CN101225301B (en) | 2008-01-15 | 2008-01-15 | Method for preparing nano hexa-aluminate based luminescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101225301A CN101225301A (en) | 2008-07-23 |
| CN101225301B true CN101225301B (en) | 2010-11-10 |
Family
ID=39857511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100172924A Expired - Fee Related CN101225301B (en) | 2008-01-15 | 2008-01-15 | Method for preparing nano hexa-aluminate based luminescent material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101225301B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795648B (en) * | 2011-05-27 | 2014-06-04 | 中国科学院过程工程研究所 | Mesoporous hexaaluminate prepared by carbon template method and having large specific surface area and preparation method of hexaaluminate |
| CN106032284B (en) * | 2015-03-09 | 2017-06-30 | 中国科学院大连化学物理研究所 | A kind of preparation method that temperature hexa-aluminate is formed with low phase |
| CN112159213B (en) * | 2020-10-29 | 2023-07-18 | 贵州赛义光电科技有限公司 | Zero-light-attenuation luminous ceramic and preparation method thereof |
-
2008
- 2008-01-15 CN CN2008100172924A patent/CN101225301B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101225301A (en) | 2008-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4210761B2 (en) | Phosphor and production method thereof | |
| CN108865130A (en) | A kind of rare earth long afterglow luminescent powder body and preparation method thereof, water-based energy storage type long afterglow luminous paint and preparation method thereof | |
| CN101225301B (en) | Method for preparing nano hexa-aluminate based luminescent material | |
| CN111057399B (en) | Preparation method of rare earth doped clay mineral-based bismuth yellow hybrid pigment with adjustable fluorescence and color | |
| CN101368098B (en) | YVO4:Eu3/YPO4 core-shell structure nano-fluorescent powder and preparation method thereof | |
| CN101792666B (en) | Rare earth phosphate nano-phosphor and preparation method thereof | |
| CN1288582A (en) | Method of preparing high brightness, small particle red emitting phosphor | |
| CN100588610C (en) | Synthesis method of nano-fluorescent powder mixed with europium yttrium phosphate-vanadate | |
| Xie et al. | Zn2SiO4: Eu3+ micro-structures: Controlled morphologies and luminescence properties | |
| CN100529012C (en) | Red solid solution Sr-In-Ti phosphor and its preparing method | |
| Wen et al. | Sol-gel processed Ce3+, Tb3+ codoped white emitting phosphors in Sr2Al2SiO7 | |
| CN101914379A (en) | Method for preparing nitrogen oxide phosphor powder | |
| Pan et al. | Synthesis and luminescence properties of Sr3MgSi2O8: Eu2+, Dy3+ by a novel silica-nanocoating method | |
| JP2001172620A (en) | Method for producing red light emitting fluorescent microparticle | |
| CN103694998B (en) | A kind of oxysulfide red long afterglow luminous material and preparation method thereof | |
| CN112500854A (en) | Processing method of silicon dioxide nanoparticles for blue-green fluorescent powder | |
| CN102337122A (en) | Silicate green fluorescent powder and preparation method thereof | |
| CN102061168A (en) | Method for improving luminosity of europium-doped yttrium oxide red fluorescent powder | |
| CN101130691B (en) | Method for improving luminous intensity of vacuum ultraviolet luminescent material with beta-Al2O3 structure | |
| CN110172347A (en) | A kind of preparation method of tungstate red fluorescent powder | |
| CN103013516B (en) | Method for preparing europium-doped yttrium phosphate-vanadate Y (V0.5, P0.5) O4:0.05Eu<3+> ultrafine fluorescent powder | |
| KR100419863B1 (en) | Preparing method for spherical red phosphor based on borates | |
| CN108130081A (en) | Ytterbium and erbium-codoped gadolinium vanadate Green upconversion luminescent is nanocrystalline and preparation method thereof | |
| CN113583672B (en) | Eu 3+ Doped composite antimonate red fluorescent powder and preparation method and application thereof | |
| KR100447936B1 (en) | Green emitting phosphor by VUV excitiation and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: NANTONG SUZHONG TEXTILE CO., LTD. Free format text: FORMER OWNER: XI'AN UNIV. OF SCIENCE AND ENGINEERING Effective date: 20130821 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 710048 XI'AN, SHAANXI PROVINCE TO: 226600 NANTONG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130821 Address after: 226600, Nantong County, Jiangsu City, Haian Province, pier Town, pier West Village seven groups Patentee after: Nantong Suzhong Textile Co., Ltd. Address before: 710048 Shaanxi city of Xi'an Province Jinhua Road No. 5 Patentee before: Xi'an University of Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101110 Termination date: 20190115 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |