CN102206490B - Preparation method for core-shell structure red phosphor, and core-shell structure red phosphor prepared by using the same - Google Patents
Preparation method for core-shell structure red phosphor, and core-shell structure red phosphor prepared by using the same Download PDFInfo
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- CN102206490B CN102206490B CN 201010138322 CN201010138322A CN102206490B CN 102206490 B CN102206490 B CN 102206490B CN 201010138322 CN201010138322 CN 201010138322 CN 201010138322 A CN201010138322 A CN 201010138322A CN 102206490 B CN102206490 B CN 102206490B
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Abstract
The invention discloses a preparation method for a core-shell structure red phosphor, and the core-shell structure red phosphor prepared by using the same. The preparation method comprises: preparing silica microsphere through a StOber method; carrying out a surface modification for the silica microsphere; adopting the surface modified silica microsphere as a core, and coating a (Gd1-x, Eux)2O3 red phosphor onto the surface of the surface modified silica microsphere through a chemical precipitation to obtain the core-shell structure red phosphor, wherein a value range of x is 0.02<=x<=0.10. The preparation method for the core-shell structure red phosphor has advantages of simple technology condition, low equipment requirement and low cost. The core-shell structure red phosphor provided by the present invention has advantages of controllable particle size, uniform and single morphology, good stability and strong luminescence intensity.
Description
Technical field
The present invention relates to the luminescent material technical field, relate in particular to its nucleocapsid structure red fluorescence powder that utilizes the method to prepare of preparation method of a kind of nucleocapsid structure red fluorescence powder.
Background technology
In recent years, the rare-earth trichromatic luminescent material has been widely used in the fields such as colour TV, illumination, information display, photoelectron technology, military affairs.Developed at present green and the blue emitting material of better performances, still, the research of red illuminating material and use and but make slow progress, this be due to red illuminating material stable bad, luminous intensity is low, price is high etc., and shortcoming causes.For the problem that red fluorescence powder exists, someone has proposed to adopt design philosophy and the technology of preparing of nucleocapsid structure in red fluorescence powder, has launched preparation research low-cost, high quality red fluorescent powder.
At present, the preparation method of nucleocapsid structure luminescent material mainly contains sol-gel method, self-assembly method, a step in-situ synthesis and sonochemical method etc., wherein, to the Application and preparation of fluorescent powder with core-shell structure maximum be the Pechini sol-gel method, as document " Synthesis and characterization of SiO
2/ Gd
2O
3: Eucore-shell luminescent materials " report SiO
2/ Gd
2O
3: the preparation of Eu fluorescent powder with core-shell structure.But, the weak shortcoming of light-emitting phosphor performance that the Pechini sol-gel method has the processing condition complexity, obtains.
Summary of the invention
The technical problem to be solved in the present invention is, for the defects of prior art, provides the preparation method of the simple nucleocapsid structure red fluorescence powder of a kind of processing condition, and the nucleocapsid structure red fluorescence powder that the method prepares has the characteristics of good luminous performance.
The technical problem that the present invention further will solve is, a kind of nucleocapsid structure red fluorescence powder of good luminous performance also is provided.
In order to reach above-mentioned purpose, according to the present invention, provide a kind of preparation method of nucleocapsid structure red fluorescence powder, comprising:
Step S1: adopt
Method prepares SiO
2Microsphere suspension liquid, centrifugal, washing obtains SiO
2Microballoon is then with SiO
2Microballoon is re-dispersed in deionized water, stirs add surface-modifying agent under environment and continue to stir 2～4h, obtains the SiO of surface modification
2Microsphere suspension liquid;
Step S2: adopt chemical precipitation method at SiO
2Microsphere surface is coated with (Gd
1-x, Eu
x)
2O
3Fluorescent material, wherein, the span of x is 0.02≤x≤0.10, filtration, washing, drying are calcined 2～6h with desciccate under 800～1200 ℃, obtain the nucleocapsid structure red fluorescence powder, are designated as SiO
2@(Gd
1-x, Eu
x)
2O
3, wherein, with SiO
2Be core, (Gd
1-x, Eu
x)
2O
3Be shell ,@is for coating.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, described surface-modifying agent is preferably N, N-diethyl TMS amine, polymine, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane or N-aminoethyl-γ-aminopropyltrimethoxysilane.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, the SiO that described surface-modifying agent is front with adding surface-modifying agent
2Microsphere suspension liquid is (with SiO
2Microballoon is re-dispersed into the SiO that obtains in deionized water
2Microsphere suspension liquid) volume ratio is 0.15～3%.
In the Preparation Method of nucleocapsid structure red fluorescence powder of the present invention, preferably, described step S2 is: adopt chemical precipitation method at SiO
2Microsphere surface is coated with (Gd
1-x, Eu
x)
2O
3Fluorescent material, wherein, the span of x is 0.02≤x≤0.10, filtration, washing, drying, then duplicate packages is by (Gd
1-x, Eu
x)
2O
3Fluorescent material 1～3 time is calcined 2～6h with desciccate under 800～1200 ℃, obtain the nucleocapsid structure red fluorescence powder.That is to say, in order to increase SiO
2Microsphere surface is coated with (Gd
1-x, Eu
x)
2O
3The amount of fluorescent material, but duplicate packages is by process 1～3 time.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, described chemical precipitation method comprises the following steps:
Step S2.1: press Gd
3+And Eu
3+Mol ratio be 0.98: 0.02～0.9: 0.1 preparation Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution;
Step S2.2: the SiO of the surface modification that mixed aqueous solution and step S1 are obtained
2Microsphere suspension liquid mixes, and stirs 1～4h;
Step S2.3: take to precipitate described Gd
3+And Eu
3+Urea or oxalic acid and be dissolved in deionized water, preparation urea or oxalic acid solution, described urea or oxalic acid are with respect to described Gd
3+And Eu
3+Excessive;
Step S2.4: urea or the oxalic acid solution of step S2.3 under agitation are added drop-wise in the solution of step S2.2, and continue to stir 2～5h, then regulating the pH value is 7～10, stirs 0.5～1.5h.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, described step S2.1 is: press Gd
3+And Eu
3+Mol ratio be 0.98: 0.02～0.9: 0.1 preparation Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, wherein, Gd
3+And Eu
3+Total concn be 0.1～0.2mol/L.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, described step S2.3 is: by the described Gd of precipitation
3+And Eu
3+Excessive 1.2～5.0 times of institute's expense takes urea or oxalic acid and is dissolved in deionized water, preparation urea or oxalic acid solution, and described urea or the oxalic acid concentration in solution is 0.5～2mol/L.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, described step S2.4 is: urea or the oxalic acid solution of step S2.3 under agitation are added drop-wise in the solution of step S2.2, time for adding is 30～80min, and 2～5h is stirred in continuation, then regulating the pH value with nitric acid or ammoniacal liquor is 7～10, stirs 0.5～1.5h.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, the drying step in described step S2 is: step S2 is obtained washed product dry 2～4h under 80～100 ℃.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, preferably, the washing step in described step 2 is: with at least a washing in deionized water and ethanol.
In order to reach above-mentioned purpose, according to the present invention, also provide a kind of nucleocapsid structure red fluorescence powder, its preparation method by above-mentioned nucleocapsid structure red fluorescence powder prepares.
In the preparation method of nucleocapsid structure red fluorescence powder of the present invention, at first
Method prepares silicon dioxide microsphere, and silicon dioxide microsphere is carried out surface modification, then adopt chemical precipitation method to prepare the nucleocapsid structure red fluorescence powder, namely the silicon dioxide microsphere after the surface modification treatment is as core, through the precipitation mode at its surperficial coating fluorescent powder, thereby prepare the nucleocapsid structure red fluorescence powder.
The preparation method of nucleocapsid structure red fluorescence powder of the present invention has the characteristics such as processing condition are simple, equipment requirements is low, with low cost, and the nucleocapsid structure red fluorescence powder that obtains has stronger luminescent properties.
Nucleocapsid structure red fluorescence powder of the present invention, granular size can be controlled, pattern is evenly single, has satisfactory stability and stronger luminous intensity.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in accompanying drawing:
Fig. 1 is the SiO of the embodiment of the present invention 2
2@(Gd
0.95, Eu
0.05)
2O
3The photoluminescence spectra figure of nucleocapsid structure red fluorescence powder;
Fig. 2 is the SiO of the embodiment of the present invention 2
2@(Gd
0.95, Eu
0.05)
2O
3The luminescent spectrum figure of nucleocapsid structure red fluorescence powder under cathode-ray exciting;
Fig. 3 is the SiO of the embodiment of the present invention 3
2@(Gd
0.94, Eu
0.06)
2O
3The photoluminescence spectra figure of nucleocapsid structure red fluorescence powder;
Fig. 4 is the SiO of the embodiment of the present invention 3
2@(Gd
0.94, Eu
0.06)
2O
3The luminescent spectrum figure of nucleocapsid structure red fluorescence powder under cathode-ray exciting.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is described in further detail.
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
The preparation of silicon dioxide microsphere and surface modification
With the 1mL deionized water, 15mL dehydrated alcohol and the mixing of 1mL ammoniacal liquor are positioned in an Erlenmeyer flask, make it to mix under magnetic agitation, then drip the 0.5mL tetraethoxy, after being added dropwise to complete, continue stirring reaction 2h, obtain SiO
2The microsphere suspension liquid body; With the SiO that obtains
2The microsphere suspension liquid body is centrifugation under the condition of 12000rpm at rotating speed, to remove remaining ammoniacal liquor and residual tetraethoxy, obtains SiO with deionized water wash
2Microballoon; With the SiO that obtains
2Microballoon is re-dispersed into through ultra-sonic dispersion and obtains the 10mL silica suspension in deionized water, add 0.1mL surface-modifying agent N-aminoethyl-γ-aminopropyltrimethoxysilane in the 10mL silica suspension under the environment of magnetic agitation, then magnetic agitation 2h obtains the SiO of surface modification
2Microsphere suspension liquid is designated as A1.
SiO
2@(Gd
0.98, Eu
0.02)
2O
3The preparation of nucleocapsid structure red fluorescence powder
Press Gd (NO
3)
3: Eu (NO
3)
3Mol ratio be that the ratio of 0.98: 0.02 takes 1.774g Gd
2O
3And 0.0352gEu
2O
3, with concentrated nitric acid with Gd
2O
3And Eu
2O
3Dissolving, and be mixed with 10mL Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, Gd wherein
3+And Eu
3+Total concn be 0.5mol/L; With Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution join in the A1 solution that obtains previously, magnetic agitation 1h, this moment, the mixed solution that obtains was designated as B1; Then take 1.5306g urea by excessive 5 times of urea, and urea is dissolved in the 25.5mL deionized water, obtain the urea soln that concentration is 1mol/L; Urea soln is added drop-wise in B1 solution obtained above under magnetic agitation, time for adding is 30min, drips rear continuation magnetic agitation 2h, and the pH with reaction system is adjusted to 7 with nitric acid afterwards, and then magnetic agitation 1.5h, the suspension that obtain this moment is designated as C1; C1 is filtered, use deionized water wash, and the filtration product after washing is placed on dry 4h in the baking oven of 80 ℃; Replace A1 with desciccate, the coating process is repeated 3 times, the desciccate that then will finally obtain finally can obtain SiO at 800 ℃ of lower soak calcining 6h
2@(Gd
0.98, Eu
0.02)
2O
3The nucleocapsid structure red fluorescence powder.
Embodiment 2
The preparation of silicon dioxide microsphere and surface modification
With the 10mL deionized water, 25mL dehydrated alcohol and the mixing of 4mL ammoniacal liquor are positioned in an Erlenmeyer flask, make it to mix under magnetic agitation, then drip the 1mL tetraethoxy, after being added dropwise to complete, continue stirring reaction 3h, obtain SiO
2The microsphere suspension liquid body; With the SiO that obtains
2The microsphere suspension liquid body is centrifugation under the condition of 12000rpm at rotating speed, to remove remaining ammoniacal liquor and residual tetraethoxy, obtains SiO with deionized water wash
2Microballoon; With the SiO that obtains
2Microballoon is re-dispersed into through ultra-sonic dispersion and obtains the 10mL silica suspension in deionized water, add 0.3mL surface-modifying agent 3-aminopropyl trimethoxysilane in the 10mL silica suspension under the environment of magnetic agitation, then magnetic agitation 2h obtains the SiO of surface modification
2Microsphere suspension liquid is designated as A2.
SiO
2@(Gd
0.95, Eu
0.05)
2O
3The preparation of nucleocapsid structure red fluorescence powder
Press Gd (NO
3)
3: Eu (NO
3)
3Mol ratio be that the ratio of 0.95: 0.05 takes 3.620g Gd
2O
3And 0.1853gEu
2O
3, with concentrated nitric acid with Gd
2O
3And Eu
2O
3Dissolving, and be mixed with 20mL Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, Gd wherein
3+And Eu
3+Total concn be 0.53mol/L; With Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution join in the A2 solution that obtains previously, magnetic agitation 2h, this moment, the mixed solution that obtains was designated as B2; Then take 2.3874g oxalic acid by excessive 1.2 times of oxalic acid, and oxalic acid is dissolved in the 18.9mL deionized water, obtain the oxalic acid solution that concentration is 1mol/L; Oxalic acid solution is added drop-wise under magnetic agitation in B2 solution obtained above, and time for adding is 40min, drips rear continuation magnetic agitation 3h, and the pH with reaction system is adjusted to 9 with ammoniacal liquor afterwards, and then magnetic agitation 1h, and the suspension that obtain this moment is designated as C2; C2 is filtered, use washing with alcohol, and will wash dry 2h in the baking oven that filtration product after washing is placed on 100 ℃; The desciccate that obtains is calcined 4h 1000 ℃ of lower soaks, finally can obtain SiO
2@(Gd
0.95, Eu
0.05)
2O
3The nucleocapsid structure red fluorescence powder.
Fig. 1 is the SiO of the embodiment of the present invention 2
2@(Gd
0.95, Eu
0.05)
2O
3The photoluminescence spectra figure of nucleocapsid structure red fluorescence powder.Fig. 2 is the SiO of the embodiment of the present invention 2
2@(Gd
0.95, Eu
0.05)
2O
3The luminescent spectrum figure of nucleocapsid structure red fluorescence powder under cathode-ray exciting.Can be found out by Fig. 1 and Fig. 2, the nucleocapsid structure red fluorescence powder that the present embodiment prepares all has good luminescent properties under photoluminescence and cathode-ray exciting.
Embodiment 3
The preparation of silicon dioxide microsphere and surface modification
10mL deionized water, 30mL dehydrated alcohol and 6mL ammoniacal liquor are mixed being positioned in an Erlenmeyer flask, make it to mix under magnetic agitation, then drip the 2mL tetraethoxy, after being added dropwise to complete, continue stirring reaction 3h, obtain SiO
2The microsphere suspension liquid body; With the SiO that obtains
2The microsphere suspension liquid body is the condition reason centrifugation of 12000rpm at rotating speed, to remove remaining ammoniacal liquor and residual positive silicon ester ethyl ester, obtains SiO with deionized water wash
2Microballoon; With the SiO that obtains
2Microballoon is re-dispersed into through ultra-sonic dispersion and obtains the 20mL silica suspension in deionized water, adds 0.2mL surface-modifying agent polymine under the environment of magnetic agitation in the 20mL silica suspension, and magnetic agitation 2h then obtains the SiO of surface modification
2Microsphere suspension liquid is designated as A3.
SiO
2@(Gd
0.94, Eu
0.06)
2O
3The preparation of nucleocapsid structure red fluorescence powder
Press Gd (NO
3)
3: Eu (NO
3)
3Mol ratio be that the ratio of 0.94: 0.06 takes 4.344g Gd
2O
3With 0.2996g Eu
2O
3, with concentrated nitric acid with Gd
2O
3And Eu
2O
3Dissolving, and be mixed with 20mL Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, Gd wherein
3+And Eu
3+Total concn be 0.638mol/L; With Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution join in the A3 solution that obtains previously, magnetic agitation 2h, this moment, the mixed solution that obtains was designated as B3; Then take 3.150g oxalic acid by excessive 1.3 times of oxalic acid, and oxalic acid is dissolved in the 50mL deionized water, obtain the oxalic acid solution that concentration is 0.5mol/L; Oxalic acid solution is added drop-wise under magnetic agitation in B3 solution obtained above, and time for adding is 60min, drips rear continuation magnetic agitation 3h, and the pH with reaction system is adjusted to 9 with ammoniacal liquor afterwards, and then magnetic agitation 1h, and the suspension that obtain this moment is designated as C3; C3 is filtered, and with deionized water and ethanol filtration washing, and the filtration product after washing is placed on dry 3h in the baking oven of 90 ℃; The dry substance that obtains is calcined 4h 1000 ℃ of lower soaks, finally can obtain SiO
2@(Gd
0.94, Eu
0.06)
2O
3The nucleocapsid structure red fluorescence powder.
Fig. 3 is the SiO of the embodiment of the present invention 3
2@(Gd
0.94, Eu
0.06)
2O
3The photoluminescence spectra figure of nucleocapsid structure red fluorescence powder.Fig. 4 is the SiO of the embodiment of the present invention 3
2@(Gd
0.94, Eu
0.06)
2O
3The luminescent spectrum figure of nucleocapsid structure red fluorescence powder under cathode-ray exciting.Can be found out by Fig. 3 and Fig. 4, the nucleocapsid structure red fluorescence powder of the present embodiment preparation all has good luminescent properties under photoluminescence and cathode-ray exciting.
Embodiment 4
The preparation of silicon dioxide microsphere and surface modification
15mL deionized water, 40mL dehydrated alcohol and 7mL ammoniacal liquor are mixed being positioned in an Erlenmeyer flask, make it to mix under magnetic agitation, then drip the 4mL tetraethoxy, after being added dropwise to complete, continue stirring reaction 4h, obtain SiO
2The microsphere suspension liquid body; With the SiO that obtains
2The microsphere suspension liquid body is centrifugation under the condition of 12000rpm at rotating speed, to remove remaining ammoniacal liquor and residual positive estersil ethyl ester, obtains SiO with deionized water wash
2Microballoon; With the SiO that obtains
2Microballoon is re-dispersed into through ultra-sonic dispersion and obtains the 30mL silica suspension in deionized water, add 0.4mL surface-modifying agent 3-aminopropyl triethoxysilane in the 30mL silica suspension under the environment of magnetic agitation, then magnetic agitation 2h obtains the SiO of surface modification
2Microsphere suspension liquid is designated as A4.
SiO
2@(Gd
0.92, Eu
0.08)
2O
3The preparation of nucleocapsid structure red fluorescence powder
Press Gd (NO
3)
3: Eu (NO
3)
3Mol ratio be that the ratio of 0.92: 0.08 takes 7.240g Gd
2O
3With 0.6121g Eu
2O
3, with concentrated nitric acid with Gd
2O
3And Eu
2O
3Dissolving, and be mixed with 21.7mL Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, Gd wherein
3+And Eu
3+Total concn be 1mol/L; With the Gd (NO that obtains
3)
3And Eu (NO
3)
3Mixed aqueous solution join in the A4 solution that obtains previously, magnetic agitation 3h, this moment, the mixed solution that obtains was designated as B4; Then take 5.752g oxalic acid by excessive 1.4 times of oxalic acid, and oxalic acid is dissolved in the 25mL deionized water, obtain the oxalic acid solution that concentration is 1.83mol/L; Oxalic acid solution is added drop-wise in B4 solution obtained above under magnetic agitation, time for adding is 70min, drips rear continuation magnetic agitation 4h, and the pH with reaction system is adjusted to 11 with ammoniacal liquor afterwards, and then magnetic agitation 0.5h, the suspension that obtain this moment is designated as C4; C4 is filtered, use deionized water wash, and the filtration product after washing is placed on dry 2h in the baking oven of 100 ℃; The desciccate that obtains is calcined 3h 1100 ℃ of lower soaks, finally can obtain SiO
2@(Gd
0.92, Eu
0.08)
2O
3The nucleocapsid structure red fluorescence powder.
Embodiment 5
The preparation of silicon dioxide microsphere and surface modification
20mL deionized water, 50mL dehydrated alcohol and 9mL ammoniacal liquor are mixed being positioned in an Erlenmeyer flask, make it to mix under magnetic agitation, then drip the 6mL tetraethoxy, after being added dropwise to complete, continue stirring reaction 6h, obtain SiO
2The microsphere suspension liquid body; With the SiO that obtains
2The microsphere suspension liquid body is centrifugation under the condition of 12000rpm at rotating speed, to remove remaining ammoniacal liquor and residual positive estersil ethyl ester, obtains SiO with deionized water wash
2Microballoon; With the SiO that obtains
2Microballoon is re-dispersed into through ultra-sonic dispersion and obtains the 40mL silica suspension in deionized water, add 0.06mL surface-modifying agent N in the 10mL silica suspension under the environment of magnetic agitation, N-diethyl TMS amine, magnetic agitation 4h then obtains the SiO of surface modification
2Microsphere suspension liquid is designated as A5.
SiO
2@(Gd
0.90, Eu
0.1)
2O
3The preparation of nucleocapsid structure red fluorescence powder
Press Gd (NO
3)
3: Eu (NO
3)
3Mol ratio be that the ratio of 0.90: 0.10 takes 9.774g Gd
2O
3With 1.056g Eu
2O
3, with concentrated nitric acid with Gd
2O
3And Eu
2O
3Dissolving, and be mixed with 15mL Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, Gd wherein
3+And Eu
3+Total concn be 2mol/L; With Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution join in the A5 liquid that obtains previously, magnetic agitation 4h, this moment, the mixed solution that obtains was designated as B5; Then take 8.505g oxalic acid by excessive 1.5 times of oxalic acid, and oxalic acid is dissolved in the 34mL deionized water, obtain the oxalic acid solution that concentration is 2mol/L; Oxalic acid solution is added drop-wise in B5 solution obtained above under magnetic agitation, time for adding is 80min, drips rear continuation magnetic agitation 5h, and the pH with reaction system is adjusted to 12 with ammoniacal liquor afterwards, and then magnetic agitation 0.5h, the suspension that obtain this moment is designated as C5; C5 is filtered, use washing with alcohol, and the filtration product after washing is placed on dry 3h in the baking oven of 100 ℃; The desciccate that obtains is calcined 2h 1200 ℃ of lower soaks, finally can obtain SiO
2@(Gd
0.90, Eu
0.10)
2O
3The nucleocapsid structure red fluorescence powder.
The above is only representative embodiment of the present invention, does not limit the present invention in any way, and all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces or improvement etc., within all should being included in protection scope of the present invention.
For example, in order to increase the coating of fluorescent material outer shell, the coating process can be repeated 1 time, 2 times or 4 times.
Claims (8)
1. the preparation method of a nucleocapsid structure red fluorescence powder, is characterized in that, comprising:
Step S1: adopt
Method prepares SiO
2Microsphere suspension liquid, centrifugal, washing obtains SiO
2Microballoon is then with SiO
2Microballoon is re-dispersed in deionized water, stirs add surface-modifying agent under environment and continue to stir 2～4h, obtains the SiO of surface modification
2Microsphere suspension liquid;
Step S2: adopt chemical precipitation method at SiO
2Microsphere surface is coated with (Gd
1-x, Eu
x)
2O
3Fluorescent material, wherein, the span of x is 0.02≤x≤0.10, filtration, washing, drying, then duplicate packages is by (Gd
1-x, Eu
x)
2O
3Fluorescent material 1～3 time is calcined 2～6h with desciccate under 800～1200 ℃, obtain the nucleocapsid structure red fluorescence powder;
Described chemical precipitation method comprises the following steps:
Step S2.1: press Gd
3+And Eu
3+Mol ratio be 0.98: 0.02～0.9: 0.1 preparation Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution;
Step S2.2: the SiO of the surface modification that mixed aqueous solution and step S1 are obtained
2Microsphere suspension liquid mixes, and stirs 1～4h;
Step S2.3: take to precipitate described Gd
3+And Eu
3+Urea or oxalic acid and be dissolved in deionized water, preparation urea or oxalic acid solution, described urea or oxalic acid are with respect to described Gd
3+And Eu
3+Excessive;
Step S2.4: urea or the oxalic acid solution of step S2.3 under agitation are added drop-wise in the solution of step S2.2, continue to stir 2～5h, then regulating the pH value is 7～10, stirs 0.5～1.5h.
2. the preparation method of nucleocapsid structure red fluorescence powder according to claim 1, it is characterized in that, described surface-modifying agent is N, N-diethyl TMS amine, polymine, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane or N-aminoethyl-γ-aminopropyltrimethoxysilane.
3. the preparation method of nucleocapsid structure red fluorescence powder according to claim 1 and 2, is characterized in that, the SiO that described surface-modifying agent is front with adding described surface-modifying agent
2The microsphere suspension liquid volume ratio is 0.15～3%.
4. the preparation method of nucleocapsid structure red fluorescence powder according to claim 1, is characterized in that, described step S2.1 is: press Gd
3+And Eu
3+Mol ratio be 0.98: 0.02～0.9: 0.1 preparation Gd (NO
3)
3And Eu (NO
3)
3Mixed aqueous solution, wherein, Gd
3+And Eu
3+Total concn be 0.1～0.2mol/L.
5. the preparation method of nucleocapsid structure red fluorescence powder according to claim 1, is characterized in that, described step S2.3 is: by the described Gd of precipitation
3+And Eu
3+Excessive 1.2～5.0 times of institute's expense takes urea or oxalic acid and is dissolved in deionized water, preparation urea or oxalic acid solution, and described urea or the oxalic acid concentration in solution is 0.5～2mol/L.
6. the preparation method of nucleocapsid structure red fluorescence powder according to claim 5, it is characterized in that, described step S2.4 is: urea or the oxalic acid solution of step S2.3 under agitation are added drop-wise in the solution of step S2.2, time for adding is 30～80min, and 2～5h is stirred in continuation, then regulating the pH value with nitric acid or ammoniacal liquor is 7～10, stirs 0.5～1.5h.
7. the preparation method of nucleocapsid structure red fluorescence powder according to claim 1, is characterized in that, the drying step in described step S2 is: the washed product that step S2 is obtained is dry 2～4h under 80～100 ℃.
8. a nucleocapsid structure red fluorescence powder, is characterized in that, prepared by the preparation method of the described nucleocapsid structure red fluorescence powder of claim 1～7 any one.
Priority Applications (1)
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| CN108949178A (en) * | 2017-05-19 | 2018-12-07 | 上海汉邦普净节能科技有限公司 | Embedded photoluminescent material |
| CN108997998A (en) * | 2017-06-06 | 2018-12-14 | 深圳市光峰光电技术有限公司 | Fluorescent powder grain of monodispersed core-shell structural and preparation method thereof |
| CN112176720B (en) * | 2020-09-28 | 2023-04-25 | 安徽瑜合警用装备有限公司 | Photoluminescent finishing agent based on silica microspheres, preparation method and application thereof |
| CN112846173A (en) * | 2021-02-08 | 2021-05-28 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide powder for X, gamma ray protection |
| CN113789169B (en) * | 2021-10-29 | 2024-01-26 | 重庆文理学院 | Fluorescent powder and preparation method thereof |
| CN116836698B (en) * | 2023-05-11 | 2024-06-11 | 安徽工业大学 | Silicon dioxide long afterglow luminescent material, preparation method, anti-counterfeiting coating and application |
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