CN117801820A - Red long afterglow material and preparation method thereof - Google Patents
Red long afterglow material and preparation method thereof Download PDFInfo
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- CN117801820A CN117801820A CN202311836897.7A CN202311836897A CN117801820A CN 117801820 A CN117801820 A CN 117801820A CN 202311836897 A CN202311836897 A CN 202311836897A CN 117801820 A CN117801820 A CN 117801820A
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- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 239000011777 magnesium Substances 0.000 claims abstract description 29
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 27
- -1 magnesium halide Chemical class 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000007873 sieving Methods 0.000 claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 239000010431 corundum Substances 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 9
- 230000002688 persistence Effects 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 7
- 150000004820 halides Chemical class 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 238000011946 reduction process Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000012856 weighed raw material Substances 0.000 description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
- C09K11/7789—Oxysulfides
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- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a red long afterglow material and a preparation method thereof, the red long afterglow material of the invention mainly comprises Ln 2 O 3 、S、TiO 2 、Eu 2 O 3 Is prepared by doping magnesium halide into raw materials. The preparation method of the red long afterglow material comprises the following steps: raw material Ln 2 O 3 、S、TiO 2 、Eu 2 O 3 Weighing according to the corresponding stoichiometric ratio of the final product structure, doping magnesium halide, adding a fluxing agent Na 2 CO 3 Mixing and stirring uniformly to obtain a mixture; filling the mixture into a corundum crucible for presintering, and reducing and burning by hydrogen; and sieving the powder obtained by presintering, filling the powder into a corundum crucible again, performing secondary sintering, cooling along with a furnace, and taking out the powder. By adopting the red long afterglow material of the invention and adopting halides such as MgF, mgCl and the like as magnesium sources, mg ions are efficiently doped, thereby avoiding the problem of low Mg ion doping efficiency caused by adopting MgO as the magnesium source in the past.
Description
Technical Field
The invention relates to the field of fluorescent powder preparation, in particular to a red long afterglow material and a preparation method thereof.
Background
The long afterglow fluorescent powder on the market at present mainly takes the cold colors such as yellow green, sky blue and the like as the main materials. The long persistence of warm color such as orange and red is not good in the market due to low brightness, short persistence time, serious light decay, insufficient stability, high cost and the like. The warm color has higher recognition degree, and can play a role in emphasis and beautification when applied to the safety field and the decoration field. Is that the prior art limits the development of long persistence of warm color, which leads to the market demand not being completely released. Therefore, it is necessary to develop a long afterglow of warm color with high brightness and long afterglow time.
The sulfur oxide system compound is most representative in the warm color long afterglow, has optimal performance in various warm color long afterglow, and solves the problem that the primary sulfide system is easy to deliquesce to release hydrogen sulfide. The brightness is high and the stability is good. The afterglow time can be maintained for 5 hours, the luminous color is bright and adjustable, and the afterglow time can be changed from orange to red. The traditional sulfur oxide red long afterglow is formed by Y 2 O 3 、S、TiO 2 、Eu 2 O 3 MgO as raw material, na 2 CO 3 Is prepared by crushing, pickling and ball milling the fluxing agent after the fluxing agent is reduced at the high temperature of 1200-1300 ℃. Long afterglow of up to 10 hours compared to yellowish green, bluish green, afterglow times of 1000mcd/m 2 The afterglow brightness of the above is far from comparable with that of the long afterglow performance of the oxysulfide, and the afterglow performance of the oxysulfide cannot reach the commercial level, and besides the structural limitation, the process of the afterglow luminance is not kept up.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a red long afterglow material, which uses halides such as MgF and MgCl as magnesium sources, and efficiently dopes Mg ions, so as to avoid the problem of low doping efficiency of Mg ions due to the adoption of MgO as magnesium source in the past.
The second object of the present invention is to provide a method for preparing the above red long afterglow material, which adopts the technology of a staged reduction process, reduces the hardening speed of powder at a low temperature, and has enough time, space and H 2 Fully reacting CO reduction; then the mixture is subjected to secondary high temperatureThe original method ensures the full reaction of the powder and avoids the problem that the original reduction does not fully influence the brightness and stability of the material.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a red long afterglow material, which mainly comprises Ln 2 O 3 、S、TiO 2 、Eu 2 O 3 Is prepared by doping magnesium halide into raw materials.
Preferably, as a further embodiment, the specific chemical formula is Ln 2 O 2 S, xEu, yTi, wherein x and y are mole fractions, and the values of x and y are as follows: x is more than or equal to 0.01 and less than or equal to 0.1, Y is more than or equal to 0.01 and less than or equal to 0.05, and Ln is at least one or two of Y, la and Gd.
Preferably, as a further embodiment, the doped magnesium halide is MgF, mgCl or a mixture of both.
Preferably, as a further implementation manner, a mixture of two kinds of MgF and MgCl is adopted, and more preferably the mass ratio between MgF and MgCl when doped is (1-3): 1.
the invention provides a formula of a red long afterglow material and a preparation method thereof, and the preparation method comprises the following steps:
raw material Ln 2 O 3 、S、TiO 2 、Eu 2 O 3 Weighing according to the corresponding stoichiometric ratio of the final product structure, doping magnesium halide, adding a fluxing agent Na 2 CO 3 Mixing and stirring uniformly to obtain a mixture;
filling the mixture into a corundum crucible, presintering in a high-temperature tunnel furnace, wherein the sintering temperature is 1100-1200 ℃, the sintering time is 2-4 h, and reducing and burning by hydrogen;
sieving the powder obtained by presintering, filling the powder into a corundum crucible again, carrying out secondary sintering on a carbon placing block in a high-temperature furnace, wherein the sintering temperature is 1300-1400 ℃, the sintering time is 2-4 h, and introducing N 2 And (5) taking out the powder after cooling along with the furnace to obtain the protective atmosphere.
Preferably, as a further implementation scheme, the powder taken out after cooling along with the furnace is placed in hydrochloric acid solution with the pH less than or equal to 2 and stirred for 0.5 to 1h, the redundant S impurities are removed, and the pH is adjusted to be neutral by washing with hot water for multiple times.
Preferably, as a further implementation scheme, after the pH is adjusted to be neutral, the powder is dehydrated, dried and sieved.
Preferably, as a further embodiment, the temperature of the presintering is controlled between 1150-1180 ℃ and the sintering time is 2.5-3h.
Preferably, as a further embodiment, the secondary sintering is carried out at a temperature of 1350-1380 ℃ for a sintering time of 2.5-3 hours.
Preferably, as a further embodiment, the doped magnesium halide is mixed with Ln 2 O 3 The molar ratio between the two is (0.02-0.08): 1.
The invention relates to a red long afterglow material and a preparation method thereof, wherein the preparation method adopts a graded reduction process, and magnesium halide is used as a magnesium source to dope Mg ions, so that Ln with high brightness and good afterglow performance is finally prepared 2 O 2 The Eu red long afterglow fluorescent powder has the advantages compared with the prior art: adopting a grading reduction process; fully reducing the mixture by a primary low-temperature reduction and a secondary high-temperature reduction process; the method takes halides such as MgF, mgCl and the like as magnesium sources, and efficiently dopes Mg ions, and particularly, the optimal scheme is a mode of mixing and doping MgF and MgCl in the doping process. Different halides can play different roles at different stages of phase formation. MgCl with low melting point can promote the system to melt during low-temperature reduction, so that reactants contact completely and Mg at low temperature 2+ At this stage, light-emitting centers can be formed into the light-emitting matrix; the MgF with high melting point can fully permeate into the system in the second high-temperature reduction, so as to promote the high-temperature reduction reaction to fully proceed, and Mg 2+ Evenly distributed in the system. Therefore, in order to better match the halide with the two-step reduction reaction, it is preferable to use a method of mixing and doping the two halides.
In addition, through further practice, the added magnesium halide type is except that MgF and MgCl are specifically selected, and the strength of the fluorescent powder can be further improved after the MgF and MgCl are mixed according to a certain mass ratio when being taken, so that the composite flux system can improve the doping rate of Mg ions, substances in a molten state in the system are promoted to be increased in different reactions, the Mg ions are more completely contacted with other reactants, and the crystallization of the product is more complete. The crystallization integrity can promote the luminous intensity of the fluorescent powder to be improved, so that the balance of the addition amount of the fluorescent powder and the fluorescent powder is best pursued, and the luminous intensity can be improved by controlling the addition amount of the fluorescent powder and the fluorescent powder within a proper mass ratio range.
Compared with the prior art, the invention has the beneficial effects that:
(1) The red long afterglow material of the invention is different from the prior formula, and Ln with high brightness and good afterglow performance is prepared by doping MgF, mgCl and other halides as magnesium sources 2 O 2 S, eu red long afterglow fluorescent powder.
(2) The preparation method of the red long afterglow material has the advantages of tight step operation connection, low operation condition and adoption of a graded reduction process; the fluorescent powder is fully reduced by a primary low-temperature reduction and secondary high-temperature reduction process, so that the performance of the prepared fluorescent powder is improved.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
1) According to Y 2 O 3 :1mol、S:1.54mol、TiO 2 :0.01mol、Eu 2 O 3 : the raw materials are weighed according to the proportion of 0.01mol, 0.02mol of MgCl is doped, and 0.07mol of Na is added 2 CO 3 As a fluxing agent. Uniformly mixing the weighed raw materials, filling the mixture into a corundum crucible, opening 6 holes, and covering a crucible cover; first firingSintering (presintering) is carried out in a high-temperature tunnel furnace, the sintering temperature is 1100 ℃, the heat preservation time is 4 hours, and hydrogen is reduced and burned; sieving the powder obtained by presintering, filling the powder into a corundum crucible again, opening 6 holes, and placing carbon blocks into a high-temperature furnace for secondary sintering; sintering temperature is 1300 ℃, heat preservation time is 2h, and N is introduced 2 And (3) preparing a protective atmosphere, cooling with a furnace, taking out, and sieving with a jaw crusher and a pair of rollers to obtain powder.
2) Y prepared in step 1) 2 O 2 The S powder is placed in hydrochloric acid solution with pH less than or equal to 2 and stirred for 0.5 to 1h, redundant S impurities are removed, and the pH is adjusted to be neutral by washing with hot water for multiple times.
3) Dehydrating the powder treated in the step 2), drying, and finally sieving to obtain Y 2 O 2 S is 0.01Eu:0.01Ti red long afterglow.
Example 2
1) According to Y 2 O 3 :1mol、S:1.54mol、TiO 2 :0.1mol、Eu 2 O 3 : the raw materials are respectively weighed according to the proportion of 0.1mol, 0.05mol of MgF is doped, and 0.07mol of Na is added 2 CO 3 As a fluxing agent. Uniformly mixing the weighed raw materials, filling the mixture into a corundum crucible, opening 6 holes, and covering a crucible cover; the primary sintering (presintering) is carried out in a high-temperature tunnel furnace, the sintering temperature is 1200 ℃, the heat preservation time is 2h, and the hydrogen is reduced and burned; sieving the powder obtained by presintering, filling the powder into a corundum crucible again, opening 6 holes, and placing carbon blocks into a high-temperature furnace for secondary sintering; sintering temperature is 1400 ℃, heat preservation time is 4 hours, and N is introduced 2 And (3) preparing a protective atmosphere, cooling with a furnace, taking out, and sieving with a jaw crusher and a pair of rollers to obtain powder.
2) Y prepared in step 1) 2 O 2 The S powder is placed in hydrochloric acid solution with pH less than or equal to 2 and stirred for 0.5 to 1h, redundant S impurities are removed, and the pH is adjusted to be neutral by washing with hot water for multiple times.
3) Dehydrating the powder treated in the step 2), drying, and finally sieving to obtain Y 2 O 2 S is 0.1Eu to 0.1Ti red long afterglow.
Example 3
1) According to La 2 O 3 :1mol、S:1.54mol、TiO 2 :0.02mol、Eu 2 O 3 : the raw materials are respectively weighed according to the proportion of 0.03mol, a mixture of 0.02mol of MgF and MgCl is doped, the mass ratio of MgF to MgCl is 1:1, and 0.07mol of Na is added 2 CO 3 As a fluxing agent. Uniformly mixing the weighed raw materials, filling the mixture into a corundum crucible, opening 6 holes, and covering a crucible cover; the primary sintering (presintering) is carried out in a high-temperature tunnel furnace, the sintering temperature is 1150 ℃, the heat preservation time is 2.5h, and the hydrogen is reduced and burned; sieving the powder obtained by presintering, filling the powder into a corundum crucible again, opening 6 holes, and placing carbon blocks into a high-temperature furnace for secondary sintering; sintering temperature is 1380 ℃, heat preservation time is 2.5h, and N is introduced 2 And (3) preparing a protective atmosphere, cooling with a furnace, taking out, and sieving with a jaw crusher and a pair of rollers to obtain powder.
2) Y prepared in step 1) 2 O 2 The S powder is placed in hydrochloric acid solution with pH less than or equal to 2 and stirred for 0.5 to 1h, redundant S impurities are removed, and the pH is adjusted to be neutral by washing with hot water for multiple times.
3) Dehydrating the powder treated in the step 2), drying, and finally sieving to obtain La 2 O 2 S is 0.03Eu:0.02Ti red long afterglow.
Example 4
1) According to Gd 2 O 3 :1mol、S:1.54mol、TiO 2 :0.04mol、Eu 2 O 3 : the raw materials are respectively weighed according to the proportion of 0.04mol, a mixture of 0.08mol of MgF and MgCl is doped, the mass ratio of MgF to MgCl is 3:1, and 0.07mol of Na is added 2 CO 3 As a fluxing agent. Uniformly mixing the weighed raw materials, filling the mixture into a corundum crucible, opening 6 holes, and covering a crucible cover; the primary sintering (presintering) is carried out in a high-temperature tunnel furnace, the sintering temperature is 1180 ℃, the heat preservation time is 3 hours, and the hydrogen is reduced and burned; sieving the powder obtained by presintering, filling the powder into a corundum crucible again, opening 6 holes, and placing carbon blocks into a high-temperature furnace for secondary sintering; sintering temperature is 1350 ℃, heat preservation time is 3h, and N is introduced 2 And (3) preparing a protective atmosphere, cooling with a furnace, taking out, and sieving with a jaw crusher and a pair of rollers to obtain powder.
2) Y prepared in step 1) 2 O 2 S powder is placed in hydrochloric acid solution with pH less than or equal to 2 and stirred for 0.5 to 1h, and then removedAnd (3) removing redundant S impurities, and adjusting the pH value to be neutral by washing with hot water for multiple times.
3) Dehydrating the powder treated in the step 2), drying, and finally sieving to obtain Gd 2 O 2 S is 0.04Eu:0.04Ti red long afterglow.
Example 5
The specific procedure was as in example 3, except that the doped magnesium halide was MgF.
Example 6
The specific procedure is the same as in example 3 except that the doped magnesium halide is a mixture of MgF and MgCl, but the mass ratio of MgF to MgCl is 6:1.
Example 7
The specific procedure was as in example 3, except that 1mol of doped magnesium halide was used.
Comparative example 1
1) According to Y 2 O 3 :1mol、S:1.54mol、TiO 2 :0.06mol、Eu 2 O 3 :0.024mol, mgO: the raw materials were weighed at a ratio of 0.04mol, and 0.07mol of Na was added 2 CO 3 As a fluxing agent. Uniformly mixing the weighed raw materials, filling the mixture into a corundum crucible, opening 6 holes, placing carbon blocks, and sending the mixture into a high-temperature furnace for sintering; sintering at 1300-1400 deg.c for 2-4 hr and introducing N 2 Taking out the powder after cooling along with the furnace, and crushing and sieving the powder to obtain the protective atmosphere.
2) Y prepared in step 1) 2 O 2 The S powder is placed in hydrochloric acid solution with pH less than or equal to 2 and stirred for 0.5 to 1h, redundant S impurities are removed, and the pH is adjusted to be neutral by washing with hot water for multiple times.
3) Dehydrating the powder treated in the step 2), drying, and finally sieving to obtain Y 2 O 2 S:0.024Eu:0.06Ti:0.04MgO red long afterglow.
Experimental example 1
The specific afterglow time of the red long afterglow materials of the respective examples and comparative examples described above, the afterglow luminance was compared, and the afterglow time refers to the time at which the excitation was stopped and the emission was continued by naked eyes. The human eyes can recognizeThe luminous brightness of (C) is 0.03mcd/m 2 . Therefore, in practical test, the afterglow time means that the luminance of the light emitted after the excitation is stopped decays from an initial value to 0.03mcd/m 2 Is a time of (a) to be used. The specific detection results are shown in the following table 1:
TABLE 1 Performance test results
As can be seen from Table 1, the red long persistence of the present invention not only improves persistence brightness and prolongs the rest of the persistence time by doping magnesium halide, but also further improves persistence brightness and persistence time after magnesium halide is mixed by a specific mass ratio of magnesium halide required to be adopted after the experiment.
In addition, it is also apparent from the experimental data of example 7 that the magnesium halide added in the present invention is preferably controlled within the range of the molar ratio required in the present invention, and that the addition amount is too large or too small, which has an influence on the final effect, compared with comparative example 1 in which the magnesium halide is not doped and the two reduction is not employed, the remaining brightness and the afterglow time are not as good as those of the scheme of the present invention.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (9)
1. A red long afterglow material is characterized by that it is made up by using Ln 2 O 3 、S、TiO 2 、Eu 2 O 3 Is prepared by doping magnesium halide into raw materials.
2. The red long persistence material of claim 1, wherein the specific chemical formula is Ln 2 O 2 S, xEu, yTi, wherein x and y are mole fractions, and the values of x and y are as follows: x is more than or equal to 0.01 and less than or equal to 0.1, Y is more than or equal to 0.01 and less than or equal to 0.05, and Ln is at least one or two of Y, la and Gd.
3. The red long afterglow material of claim 1, characterized in that the doped magnesium halide is one or a mixture of two of MgF and MgCl;
preferably, the mixture of MgF and MgCl is adopted, more preferably, the mass ratio of MgF and MgCl when doped is (1-3): 1.
4. a method for preparing a red long afterglow material according to any of claims 1 to 3, characterized by comprising the steps of:
raw material Ln 2 O 3 、S、TiO 2 、Eu 2 O 3 Weighing according to the corresponding stoichiometric ratio of the final product structure, doping magnesium halide, adding a fluxing agent Na 2 CO 3 Mixing and stirring uniformly to obtain a mixture;
filling the mixture into a corundum crucible, presintering in a high-temperature tunnel furnace, wherein the sintering temperature is 1100-1200 ℃, the sintering time is 2-4 h, and reducing and burning by hydrogen;
sieving the powder obtained by presintering, filling the powder into a corundum crucible again, carrying out secondary sintering on a carbon placing block in a high-temperature furnace, wherein the sintering temperature is 1300-1400 ℃, the sintering time is 2-4 h, and introducing N 2 And (5) taking out the powder after cooling along with the furnace to obtain the protective atmosphere.
5. The preparation method according to claim 4, wherein the powder taken out after cooling with the furnace is placed in hydrochloric acid solution with pH less than or equal to 2 and stirred for 0.5-1 h, redundant S impurities are removed, and the pH is adjusted to be neutral by washing with hot water for multiple times.
6. The method according to claim 5, wherein the powder is dehydrated, dried and sieved after the pH is adjusted to neutral.
7. The method according to claim 4, wherein the temperature of the pre-firing is controlled to 1150-1180 ℃ and the sintering time is 2.5-3h.
8. The method according to claim 4, wherein the secondary sintering is carried out at 1350-1380 ℃ for 2.5-3 hours.
9. The method of claim 4, wherein the doped magnesium halide and Ln 2 O 3 The molar ratio between the two is (0.02-0.08): 1.
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| JP2005272852A (en) * | 2005-06-06 | 2005-10-06 | Nichia Chem Ind Ltd | Light emitting device |
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