CN103059840A - White ultra-long afterglow luminescent material and preparation method thereof - Google Patents
White ultra-long afterglow luminescent material and preparation method thereof Download PDFInfo
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- CN103059840A CN103059840A CN2012104289187A CN201210428918A CN103059840A CN 103059840 A CN103059840 A CN 103059840A CN 2012104289187 A CN2012104289187 A CN 2012104289187A CN 201210428918 A CN201210428918 A CN 201210428918A CN 103059840 A CN103059840 A CN 103059840A
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Abstract
The invention belongs to the field of the materials and in particular relates to a near ultraviolet and visible light excited white ultra-long afterglow luminescent material and a preparation method thereof. The general formula of the luminescent material is (M, M*O)1-x-y.(EuO)x.(MnO)y.aAl2O3.bSiO2(1). In the formula, M and M* are one or more metallic elements selected from magnesium, calcium, strontium, barium and zinc, and a, b, x and y are amount of substance and respectively meet the following formulas: 0.5<=(a+b)<=5, b=(0.1-10)a, 0.001<=x<=0.1 and 0.001<=y<=0.5. The luminescent material is a white luminescent light storing body activated by co-doping europium and manganese or co-doping europium, manganese and one or more other rare earth (RE) elements or subjecting the elements to energy transfer with other ions. The luminescent material has the beneficial effects that the sintering body has a loose structure and is easy to break; the powder grain size is about 2-5 microns; the luminescent material has good weather resistance and acid and alkali corrosion resistance and white afterglow; and the afterglow time exceeds 12 hours.
Description
Technical field
The invention belongs to Material Field, particularly white overlength afterglow luminescent material of a kind of near ultraviolet and excited by visible light and preparation method thereof.
Background technology
Fluor refers to utilize the outside stimulus effects such as particle energy, electronics, light, excites and luminous a kind of functional materials, and will still can continue luminous twinkler after stopping and being called " luminous storage material " exciting, be i.e. long after glow luminous material.Such luminescent material requires multicolor and afterglow property good in practical, good weatherability.
Hitherto known long after glow luminous material, kind is few on matrix of materials forms, and generally all is subject to luminous and the restriction of the shortcoming such as the twilight sunset energy distribution is narrower, color is dull and time of persistence is short, and weathering resistance is poor.
Take phosphor as example, at first be sulfide-based fluor, for example be (Ca, Sr) S:Bi of blue-light-emitting
3+Fluor, the luminous ZnS:Cu of yellow-green colour
2+(Zn, Cd) S:Cu fluor of fluor, emitting red light etc., maximum shortcoming is with regard to less stable, and twinkler brightness and twilight sunset life-span are also insufficient.In addition, (Zn, Cd) S: the Cu fluor contains the toxicant cadmium, uses restricted especially.ZnS:Cu
2+Fluor under wet condition, is decomposed and blackening easily by uviolizing, and time of persistence is also insufficient, and the clock and watch literal dish that uses as cheapness and refuge guide sign etc. also can only be used for indoor.Oxysalt is fluor, for example europkium-activated alkali earth metal aluminate MAl
2O
4(M is one or several of magnesium, calcium, strontium, barium here) is although have the Society such as Journal of Electrochemical, the 118th volume, the SrAl of 930 pages (1971) report
2O
4: more long-life steady persistence performance that the Eu fluor shows, still, owing to be easy to deliquescence, as luminous storage material Practical Performance or not ideal enough.The silicate fluor is as long remaining luminescent material, the problem that the ubiquity afterglow property is undesirable.On the other hand, only have maximum emission intensity with europium near 520nm/500nm as the strontium aluminate/barium aluminate salt of dominant activator, it is luminous to be yellow-green colour, and brightness decay is to 0.32mcd/m
2Time more than 2000 minutes, compare with 200 minutes of ZnS:Cu fluor, persistence characteristic is better, still, it still has the shortcomings such as the dull and weathering resistance of glow color is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of have white luminous, the steady persistence performance is good, the structure of material and performance be to the white overlength afterglow luminescent material of heat and the advantage such as chemical environment is stable, weathering resistance is good.
Another object of the present invention provides its preparation method of above-mentioned white overlength afterglow luminescent material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is (M, M
*O)
1-
X-y (EuO)
x(MnO)
y aAl
2O
3 bSiO
2(1),
M and M in the following formula
*Be expressed as the metallic element more than a kind or a kind of from magnesium, calcium, strontium, barium and zinc, selecting,
A, b, x, yBe amount of substance, satisfy respectively
0.5≦(
a+
b)≦5，
b=?(0.1～10)
a，
0.001≦
x≦0.1,
0.001≦
y≦0.5。
This luminescent material be with europium and manganese codoped or, europium, manganese and other rare earth elements RE codoped or the white luminous luminous storage material that activates with other ion generation transmission ofenergy more than a kind and a kind.
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is (M, M
*O)
1-x-k-y(EuO)
x(RE
2O
3)
k(MnO)
y aAl
2O
3 bSiO
2(2),
M and M in the following formula
*Be expressed as the metallic element more than a kind or a kind of from magnesium, calcium, strontium, barium and zinc, selecting, RE represent in rare-earth element cerium, praseodymium, neodymium, samarium, dysprosium, holmium, the ytterbium more than a kind or a kind,
A, b, x, k, yBe amount of substance, satisfy respectively
0.5≦(
a+
b)≦5，
b=?(0.1～10)
a?，
0.001≦?
x?≦0.1，
0.1≦?
k:
x?≦?3，
0.001≦
y≦0.5。
For luminescent properties and chemistry, thermostability and the weathering resistance that guarantees that luminous storage material of the present invention is good, at first determine the ratio of aluminium and silicon, the composition of aluminium and silicon should satisfy: 0.5＜=(
a+
b)＜=5,
b=(0.1～10)
aIf be in M element in this constituent with M such as a part of zinc
*Element replaces, luminous storage material steady persistence performance variation to some extent then, but improved luminosity and whiteness.
Decision is included in above-mentioned that europium in the aluminium silicon salt long after glow luminous material of the present invention forms
xValue, suitable scope be 0.001＜=
x＜=0.1.The ionic weight that becomes luminescence center is few, can not get good luminosity, if
xValue surpasses 0.1, cause follow the delustring of luminescence center interionic concentration in, or produce compound beyond the target, or the oxide compound of remaining raw material, the brightness of luminous storage material also can significantly reduce, i.e. concentration quenching.
Decision is included in above-mentioned that manganese in the aluminium silicon salt long after glow luminous material of the present invention forms
yValue, suitable scope be 0.001＜=
y＜=0.5.The ionic weight that becomes luminescence center is few, can not get good white-light emitting, if
yValue surpasses 0.5, cause follow the delustring of luminescence center interionic concentration in, or produce compound beyond the target, or the oxide compound of remaining raw material, or luminous storage material powder colour-darkening, the brightness of luminous storage material also can significantly reduce, i.e. concentration quenching.
Using the rare earth elements such as cerium, praseodymium, neodymium, samarium, dysprosium, holmium, ytterbium with europium and manganese during as co-dopant, above-mentioned
kThe scope that value should satisfy is 0.1＜=
k:
x＜=3, luminous storage material has maximum luminosity, and the steady persistence performance also improves.
A kind of preparation method of described white overlength afterglow luminescent material, the method is that raw material powder is burnt till with fusing assistant, firing condition is: under reducing atmosphere in 900～1400 ℃ of temperature constant temperature 2～4 hours, cooling is by briquetting after pulverize grinding, and in 1100～1400 ℃ of temperature constant temperature 3～8 hours, will pulverize after the sintered compact cooling under reducing atmosphere, washing, oven dry is ground, and the Powdered resultant of gained is described white overlength afterglow luminescent material;
Described raw material powder is by the compound that contains the M element, contains M
*The compound of element, the compound that contains the Al element, the compound that contains the Si element, the compound that contains the Eu element, the compound that contains the Mn element mix with the ratio of general formula (1) expression.
As preferably, described raw material powder is selected from M or M
*Or the carbonate of Mn element or subcarbonate or oxide compound, aluminum oxide or aluminium hydroxide, SiO 2 powder or metasilicic acid or orthosilicic acid, europium sesquioxide or europium carbonate or oxalic acid europium.
As preferably, when described solubility promoter was boric acid or boron oxide, consumption was the 3-4% of raw material powder weight; Described solubility promoter be ammonium halide salt or, when alkali-metal carbonate or fluorochemical, consumption is the 4-5% of raw material powder weight.
As preferably, described Powdered resultant particle diameter is 2～5 μ m.
As preferably, the washings that adopts in the described washing process is deionized water, dilute hydrochloric acid solution or ethanol.
As preferably, described reducing atmosphere is hydrogen, ammonia or carbon monoxide gas, or the gas mixture of one or several and nitrogen or argon gas wherein, or is provided by the activated carbon powder combustion method.
A kind of preparation method of described white overlength afterglow luminescent material, the method is that raw material powder is burnt till with fusing assistant, firing condition is: under reducing atmosphere in 900～1400 ℃ of temperature constant temperature 2～4 hours, cooling is by briquetting after pulverize grinding, and in 1100～1400 ℃ of temperature constant temperature 3～8 hours, will pulverize after the sintered compact cooling under reducing atmosphere, washing, oven dry is ground, and the Powdered resultant of gained is described white overlength afterglow luminescent material;
Described raw material powder is by the compound that contains the M element, contains M
*The compound of element, contain the Al element compound, contain the Si element compound, contain the Eu element compound, contain the Mn element compound and, the compound that contains rare earth elements RE more than a kind or a kind mixes with the ratio of general formula (2) expression.
As preferably, the method specifically comprises the steps:
1. the raw material powder described in the white overlength afterglow luminescent material is selected from M or M
*Or the carbonate of Mn element or subcarbonate or oxide compound, aluminum oxide or aluminium hydroxide, SiO 2 powder or metasilicic acid or orthosilicic acid, europium sesquioxide or europium carbonate or oxalic acid europium, rare-earth oxide;
2. adopting planetary ball mill that the raw material of load weighted aluminium, silicon and europium is carried out ball milling to particle diameter is 2～5 μ m;
3. the raw material with the aluminium behind the ball milling, silicon and europium carries out abundant ball milling with load weighted calcium, magnesium, strontium, barium, zinc, manganese and other rare earths material and fusing assistant, and Ball-milling Time is 10～25 hours;
4. adopt metal die will grind sufficient powdered material with two-way press moulding mode on hydropress and press knot to obtain biscuit, pressing knot pressure is 1000～5000kg/cm
2
5. biscuit is put into corundum crucible, use high temperature resistance furnace, under the reductive condition of gac or hydrogen, be heated to 900～1400 ℃ with 100～300 ℃/hour heating rate, and be incubated 2～4 hours, and drop to room temperature with 2～10 ℃/minute rate of temperature fall subsequently, obtain agglomerated material;
6. 5. the agglomerated material of gained ground 1 hour by hand, 4. get again biscuit by step, put into corundum crucible, use high temperature resistance furnace, under activated carbon grain or hydrogen reducing condition, be heated to 1100～1400 ℃ with 200～500 ℃/hour speed, constant temperature 3～8 hours, be cooled to room temperature with 2～10 ℃/minute speed subsequently, obtain agglomerated material;
7. adopting hand lapping and planetary ball mill mode to combine 6. gained agglomerated material is milled to particle size is 2～5 microns powder;
8. remove the impurity that remains in the powder with deionized water and washing with alcohol, in 80～150 ℃ of oven dry 10～30 hours, obtain the powder luminescent material;
9. adopt FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer to measure room temperature excitation spectrum and the emmission spectrum of sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker).
The invention relates to aluminosilicate white overlength afterglow luminescent material of rare earth element and manganese element doping and preparation method thereof.In detail, the invention relates to a kind of in indoor or outdoors or the medium dark place of water, can excite and produce white luminous with electron beam or ultraviolet ray or visible light or their combination, excite and still have the white long afterglow luminescent properties after stopping, and heat, chemical stability is good, aluminosilicate white overlength afterglow luminescent material take rare earth element and manganese as co-dopant and preparation method thereof.
In order to achieve the above object, the inventor is take aluminosilicate as matrix, new composition new texture twinkler is studied, obtain containing the resultant of reaction of the aluminosilicate of specific composition, with europium and manganese mix and europium and other ion generation transmission ofenergy or and other rare earth elements RE carry out codoped, the aluminosilicate series long afterglow luminescent material that preparation makes new advances.
The present invention is by selecting suitable aluminosilicate body material, doping agent collocation, fusing assistant and preparation technology successfully to prepare the aluminosilicate white overlength afterglow luminescent material of a kind of novel europium and manganese and other rare earth element codoped.
For (2～5 μ m) the Powdered white luminous aluminosilicate luminous storage material that obtains having certain particle diameter, if with boric acid or boron oxide as fusing assistant, solid solution can occur with a part of Al and replace in boron, steady persistence improves, but its replacement amount is unsuitable excessive.Superfluous boron component helps glassy phase to generate, and is unfavorable for luminosity and residual photosensitiveness.If as fusing assistant, should control the amount of fusing assistant with ammonium halide salt or alkali-metal carbonate or fluorochemical, too much fusing assistant can make the excessive sintering of luminous storage material, affects luminosity and residual photosensitiveness.
Aluminosilicate luminous storage material of the present invention is after utilizing the ultraviolet ray or visible light or their several combined dopants of electron beam or 250～430nm scope, in room temperature or more than the room temperature, shows the luminescent material of twilight sunset (fluorescence).
The main raw material of this long after glow luminous material is, contain the M element compound, contain M
*The compound of element, contain aluminium element compound, contain element silicon compound, contain the compound of europium element, the compound that contains the compound of manganese element and contain rare earth elements RE, namely contain oxide compound or oxyhydroxide or hydrated oxide or oxalate or carbonate or nitrate or the vitriol etc. of these elements.With they composition weighings by above-mentioned (1) or (2) formula, fully mix, place the heat-resisting reaction vessels such as alumina crucible or plumbago crucible.The powder crystal diffracting spectrum (XRD) of luminescent material of the present invention is seen Fig. 1.The present invention is by the suitable compatibility of luminescence center europium or manganese and rare earth elements RE and some other element, as and europium between the optimizing of the element kind such as the ion of transmission ofenergy, the ion that forms trap level, the boron that is included in the promotion particle growth in the fusing assistant, sodium, lithium and content thereof occurs, afterglow property, structural chemistry good stability, the weathering resistance that obtains having overlength is good, the emmission spectrum energy distribution is at 400～650nm, and peak value is positioned at the white luminescent material (see figure 2) of 436nm and 561nm.
Sintered body structure is loose, is easy to fragmentation, and about 2～5 μ m of powder particle size have fine weathering resistance and acid-alkali-corrosive-resisting, and twilight sunset is white in color, and time of persistence was above 12 hours.
Description of drawings
Fig. 1 is the powder crystal diffracting spectrum (XRD) of luminescent material of the present invention;
Fig. 2 is excitation spectrum and the emmission spectrum that luminescent material of the present invention records with ultraviolet courseware spectrophotometer.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation and/or change that the present invention is made all will fall into protection domain of the present invention.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
Embodiment 1:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-y(EuO)
x(MnO)
yAAl
2O
3BSiO
2(1), wherein M is Ca, and M* is Mg, a=1.0, b=1.0, x=0.05, y=0.4.
The preparation method is as follows:
Take by weighing raw material powder: CaCO
30.35mol, (MgCO
3)
4Mg (OH)
2.5H
2O 0.2mol, Eu
2O
30.05mol, MnCO
30.4mol, Al2O
3Micro mist 1mol, SiO
2Fine powder 1mol.The boric acid consumption is 3.5% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3Carrying out ball milling to particle diameter is about 2 microns, subsequently with the oxide compound mixed powder and the CaCO that obtain
3, (MgCO
3)
4Mg (OH)
2.5H
2O, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 1000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1300 ℃ of constant temperature 2 hours with 500 ℃/hour speed, be cooled to room temperature with 2 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 1500kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1200 ℃ of constant temperature 8 hours with 350 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 2:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-y(EuO)
x(MnO)
yAAl
2O
3BSiO
2(1), wherein M is Ca, and M* is Ba, a=1.0, b=2.0, x=0.05, y=0.2.
The preparation method is as follows:
Take by weighing raw material powder: CaCO
30.35mol, BaCO
30.4mol, Eu
2O
30.05mol, MnCO
30.2mol, Al2O
3Micro mist 1mol, SiO
2Fine powder 2mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3Carrying out ball milling to particle diameter is about 3 microns, subsequently with the oxide compound mixed powder and the CaCO that obtain
3, BaCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 2000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1000 ℃ of constant temperature 3 hours with 200 ℃/hour speed, be cooled to room temperature with 5 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 2000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1250 ℃ of constant temperature 6 hours with 450 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 5 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 3:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-y(EuO)
x(MnO)
yAAl
2O
3BSiO
2(1), wherein M is Sr, and M* is Zn, a=1.0, b=0.5, x=0.005, y=0.2.
The preparation method is as follows:
Take by weighing raw material powder: SrCO
30.395mol, ZnCO
30.4mol, Eu
2O
30.005mol, MnCO
30.2mol, Al2O
3Micro mist 1mol, SiO
2Fine powder 0.5mol.The boric acid consumption is 3% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3Carrying out ball milling to particle diameter is about 5 microns, subsequently with the oxide compound mixed powder and the SrCO that obtain
3, ZnCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 2500kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1050 ℃ of constant temperature 4 hours with 100 ℃/hour speed, be cooled to room temperature with 10 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 2000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1200 ℃ of constant temperature 8 hours with 450 ℃/hour speed; be cooled to room temperature with 5 ℃/minute speed subsequently; obtain sintered material; it is 4 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 4:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-y(EuO)
x(MnO)
yAAl
2O
3BSiO
2(1), wherein M is Mg, and M* is Zn, a=0.5, b=1, x=0.002, y=0.05.
The preparation method is as follows:
Take by weighing raw material powder: (MgCO
3)
4Mg (OH)
2.5H
2O 0.648mol, ZnCO
30.3mol, Eu
2O
30.002mol, MnCO
30.05mol, Al2O
3Micro mist 0.5mol, SiO
2Fine powder 1.0mol.The boric acid consumption is 3% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3Carrying out ball milling to particle diameter is about 2 microns, subsequently with the oxide compound mixed powder and the (MgCO that obtain
3)
4Mg (OH)
2.5H
2O, ZnCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 3500kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 950 ℃ of constant temperature 2 hours with 200 ℃/hour speed, be cooled to room temperature with 2 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 4000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1300 ℃ of constant temperature 4 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 5:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Ca, and M* is Zn, and Re is Ce, a=2.5, b=2.0, x=0.02, k=0.03, y=0.15.
The preparation method is as follows:
Take by weighing raw material powder: CaCO
30.6mol, ZnCO
30.2mol, Eu
2O
30.02mol, Ce
2O
30.03 mol, MnCO
30.15mol, micro mist 2.5mol, SiO
2Fine powder 2.0mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Ce
2O
3Carrying out ball milling to particle diameter is about 2 microns, subsequently with the oxide compound mixed powder and the CaCO that obtain
3, ZnCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 4500kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 950 ℃ of constant temperature 3 hours with 200 ℃/hour speed, be cooled to room temperature with 8 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 4000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1280 ℃ of constant temperature 4 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 6:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Ba, and M* is Zn, and Re is Dy, a=1.0, b=2.5, x=0.03, k=0.04, y=0.05.
The preparation method is as follows:
Take by weighing raw material powder: BaCO
30.58mol, ZnCO
30.3mol, Eu
2O
30.03mol, Dy
2O
30.04 mol, MnCO
30.05mol, Al
2O
3Micro mist 1.0mol, SiO
2Fine powder 2.5mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Dy
2O
3Carrying out ball milling to particle diameter is about 2 microns, subsequently with the oxide compound mixed powder and the BaCO that obtain
3, ZnCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 2500kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1000 ℃ of constant temperature 4 hours with 300 ℃/hour speed, be cooled to room temperature with 10 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 4000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1300 ℃ of constant temperature 5 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 4 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 7:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Sr, and M* is Zn, and Re is Nd, a=1.5, b=3.0, x=0.01, k=0.03, y=0.20.
The preparation method is as follows:
Take by weighing raw material powder: BaCO
30.36mol, ZnCO
30.4mol, Eu
2O
30.01mol, Nd
2O
30.03mol, MnCO
30.20mol, Al
2O
3Micro mist 1.5mol, SiO
2Fine powder 3.0mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Nd
2O
3Carrying out ball milling to particle diameter is about 2 microns, subsequently with the oxide compound mixed powder and the SrCO that obtain
3, ZnCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 2500kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1000 ℃ of constant temperature 4 hours with 300 ℃/hour speed, be cooled to room temperature with 10 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 4000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1300 ℃ of constant temperature 5 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 4 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 8:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Ca, and M* is Mg, and Re is Nd+Pr, a=1.0, b=4.0, x=0.03, k=0.04, y=0.20.
The preparation method is as follows:
Take by weighing raw material powder: CaCO
30.38mol, (MgCO
3)
4Mg (OH)
2.5H
2O 0.3mol, Eu
2O
30.03mol, Nd
2O
30.03mol, Pr
2O
30.01mol, MnCO
30.25mol, Al
2O
3Micro mist 1.0mol, SiO
2Fine powder 4.0mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Nd
2O
3, Pr
2O
3Carrying out ball milling to particle diameter is about 2 microns, subsequently with the oxide compound mixed powder and the CaCO that obtain
3, (MgCO
3)
4Mg (OH)
2.5H
2O, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 5000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 900 ℃ of constant temperature 3 hours with 300 ℃/hour speed, be cooled to room temperature with 5 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 4000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1350 ℃ of constant temperature 3 hours with 400 ℃/hour speed; be cooled to room temperature with 8 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 9:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Ba, and M* is Mg, and Re is Dy+Ce, a=2.0, b=3.0, x=0.04, k=0.04, y=0.30.
The preparation method is as follows:
Take by weighing raw material powder: BaCO
30.38mol, (MgCO
3)
4Mg (OH)
2.5H
2O 0.2mol, Eu
2O
30.04mol, Dy
2O
30.03mol, Ce
2O
30.01mol, MnCO
30.30mol, Al
2O
3Micro mist 2.0mol, SiO
2Fine powder 3.0mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Dy
2O
3, Ce
2O
3Carrying out ball milling to particle diameter is about 4 microns, subsequently with the oxide compound mixed powder and the BaCO that obtain
3, (MgCO
3)
4Mg (OH)
2.5H
2O, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 1000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1100 ℃ of constant temperature 2 hours with 300 ℃/hour speed, be cooled to room temperature with 5 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 2000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1400 ℃ of constant temperature 2 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 10:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Sr, and M* is Mg, and Re is Dy+Nd, a=1.0, b=3.0, x=0.02, k=0.04, y=0.10.
The preparation method is as follows:
Take by weighing raw material powder: SrCO
30.62mol, (MgCO
3)
4Mg (OH)
2.5H
2O 0.2mol, Eu
2O
30.04mol, Dy
2O
30.02mol, Nd
2O
30.02mol, MnCO
30.10mol, Al
2O
3Micro mist 1.0mol, SiO
2Fine powder 3.0mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Dy
2O
3, Ce
2O
3Carrying out ball milling to particle diameter is about 4 microns, subsequently with the oxide compound mixed powder and the SrCO that obtain
3, (MgCO
3)
4Mg (OH)
2.5H
2O, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 3000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1000 ℃ of constant temperature 3 hours with 300 ℃/hour speed, be cooled to room temperature with 8 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 3000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1200 ℃ of constant temperature 8 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 11:
A kind of white overlength afterglow luminescent material, the general formula of this luminescent material is expressed as (M, M*O)
1-x-k-y(EuO)
x(Re
2O
3)
k(MnO)
yAAl
2O
3BSiO
2(2), wherein M is Ca+Mg, and M* is Zn, and Re is Dy+Ce, a=2.0, b=2.0, x=0.02, k=0.03, y=0.10.
The preparation method is as follows:
Take by weighing raw material powder: CaCO
30.55mol, (MgCO
3)
4Mg (OH)
2.5H
2O 0.2mol, ZnCO
30.1mol, Eu
2O
30.02mol, Dy
2O
30.02mol, Ce
2O
30.01mol, MnCO
30.10mol, Al
2O
3Micro mist 2.0mol, SiO
2Fine powder 2.0mol.The boric acid consumption is 4% of raw material powder gross weight.Adopt planetary ball mill with Al
2O
3, SiO
2, Eu
2O
3, Dy
2O
3, Ce
2O
3Carrying out ball milling to particle diameter is about 4 microns, subsequently with the oxide compound mixed powder and the CaCO that obtain
3, (MgCO
3)
4Mg (OH)
2.5H
2O, ZnCO
3, MnCO
3And boric acid carries out abundant ball milling, use metal die with two-way press moulding mode with 3000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, use high temperature resistance furnace, under the hydrogen reducing condition, be heated to 1000 ℃ of constant temperature 3 hours with 300 ℃/hour speed, be cooled to room temperature with 8 ℃/minute speed subsequently, ground by hand 1 hour, again powder is used metal die with two-way press moulding mode with 3000kg/cm
2Pressure be pressed into the biscuit that diameter is 13mm; this biscuit is put into corundum crucible; use high temperature resistance furnace; under the active carbon granule reductive condition; be heated to 1200 ℃ of constant temperature 8 hours with 400 ℃/hour speed; be cooled to room temperature with 10 ℃/minute speed subsequently; obtain sintered material; it is 3 μ m that the mode that adopts hand lapping and planetary type ball-milling to combine is milled to average particle size particle size with sintered compact; remove residual impurity with deionized water and washing with alcohol; in 115 ℃ of oven dry 24 hours; make the finely dispersed luminescent material powder of particle; with room temperature excitation spectrum and the emmission spectrum of FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer mensuration sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker.).
Above-described embodiment is a kind of better scheme of the present invention, is not that the present invention is done any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (10)
1. white overlength afterglow luminescent material, it is characterized in that: the general formula of this luminescent material is (M, M
*O)
1-
X-y (EuO)
x(MnO)
y aAl
2O
3 bSiO
2(1),
M and M in the following formula
*Be expressed as the metallic element more than a kind or a kind of from magnesium, calcium, strontium, barium and zinc, selecting,
A, b, x, yBe amount of substance, satisfy respectively
0.5≦(
a+
b)≦5，
b=?(0.1～10)
a，
0.001≦
x≦0.1,
0.001≦
y≦0.5。
2. white overlength afterglow luminescent material, it is characterized in that: the general formula of this luminescent material is (M, M
*O)
1-x-k-y(EuO)
x(RE
2O
3)
k(MnO)
y aAl
2O
3 bSiO
2(2),
M and M in the following formula
*Be expressed as the metallic element more than a kind or a kind of from magnesium, calcium, strontium, barium and zinc, selecting, RE represent in rare-earth element cerium, praseodymium, neodymium, samarium, dysprosium, holmium, the ytterbium more than a kind or a kind,
A, b, x, k, yBe amount of substance, satisfy respectively
0.5≦(
a+
b)≦5，
b=?(0.1～10)
a?，
0.001≦?
x?≦0.1，
0.1≦?
k:
x?≦?3，
0.001≦
y≦0.5。
3. the preparation method of a white overlength afterglow luminescent material claimed in claim 1, it is characterized in that the method is: raw material powder is burnt till with fusing assistant, firing condition is: under reducing atmosphere in 900～1400 ℃ of temperature constant temperature 2～4 hours, cooling is ground rear briquetting by pulverizing, under reducing atmosphere in 1100～1400 ℃ of temperature constant temperature 3～8 hours, to pulverize after the sintered compact cooling, washing, oven dry, grind, the Powdered resultant of gained is described white overlength afterglow luminescent material;
Described raw material powder is by the compound that contains the M element, contains M
*The compound of element, the compound that contains the Al element, the compound that contains the Si element, the compound that contains the Eu element, the compound that contains the Mn element mix with the ratio of general formula (1) expression.
4. preparation method according to claim 3, it is characterized in that: described raw material powder is selected from M or M
*Or the carbonate of Mn element or subcarbonate or oxide compound, aluminum oxide or aluminium hydroxide, SiO 2 powder or metasilicic acid or orthosilicic acid, europium sesquioxide or europium carbonate or oxalic acid europium.
5. preparation method according to claim 3, it is characterized in that: when described solubility promoter was boric acid or boron oxide, consumption was the 3-4% of raw material powder weight; Described solubility promoter be ammonium halide salt or, when alkali-metal carbonate or fluorochemical, consumption is the 4-5% of raw material powder weight.
6. preparation method according to claim 3, it is characterized in that: described Powdered resultant particle diameter is 2～5 μ m.
7. preparation method according to claim 3, it is characterized in that: the washings that adopts in the described washing process is deionized water, dilute hydrochloric acid solution or ethanol.
8. preparation method according to claim 3, it is characterized in that: described reducing atmosphere is hydrogen, ammonia or carbon monoxide gas, or the gas mixture of one or several and nitrogen or argon gas wherein, or is provided by the activated carbon powder combustion method.
9. the preparation method of a white overlength afterglow luminescent material claimed in claim 2, it is characterized in that the method is: raw material powder is burnt till with fusing assistant, firing condition is: under reducing atmosphere in 900～1400 ℃ of temperature constant temperature 2～4 hours, cooling is ground rear briquetting by pulverizing, under reducing atmosphere in 1100～1400 ℃ of temperature constant temperature 3～8 hours, to pulverize after the sintered compact cooling, washing, oven dry, grind, the Powdered resultant of gained is described white overlength afterglow luminescent material;
Described raw material powder is by the compound that contains the M element, contains M
*The compound of element, contain the Al element compound, contain the Si element compound, contain the Eu element compound, contain the Mn element compound and, the compound that contains rare earth elements RE more than a kind or a kind mixes with the ratio of general formula (2) expression.
10. preparation method according to claim 9 is characterized in that specifically comprising the steps:
1. the raw material powder described in the white overlength afterglow luminescent material is selected from M or M
*Or the carbonate of Mn element or subcarbonate or oxide compound, aluminum oxide or aluminium hydroxide, SiO 2 powder or metasilicic acid or orthosilicic acid, europium sesquioxide or europium carbonate or oxalic acid europium, rare-earth oxide;
2. adopting planetary ball mill that the raw material of load weighted aluminium, silicon and europium is carried out ball milling to particle diameter is 2～5 μ m;
3. the raw material with the aluminium behind the ball milling, silicon and europium carries out abundant ball milling with load weighted calcium, magnesium, strontium, barium, zinc, manganese and other rare earths material and fusing assistant, and Ball-milling Time is 10～25 hours;
4. adopt metal die will grind sufficient powdered material with two-way press moulding mode on hydropress and press knot to obtain biscuit, pressing knot pressure is 1000～5000kg/cm
2
5. biscuit is put into corundum crucible, use high temperature resistance furnace, under the reductive condition of gac or hydrogen, be heated to 900～1400 ℃ with 100～300 ℃/hour heating rate, and be incubated 2～4 hours, and drop to room temperature with 2～10 ℃/minute rate of temperature fall subsequently, obtain agglomerated material;
6. 5. the agglomerated material of gained ground 1 hour by hand, 4. get again biscuit by step, put into corundum crucible, use high temperature resistance furnace, under activated carbon grain or hydrogen reducing condition, be heated to 1100～1400 ℃ with 200～500 ℃/hour speed, constant temperature 3～8 hours, be cooled to room temperature with 2～10 ℃/minute speed subsequently, obtain agglomerated material;
7. adopting hand lapping and planetary ball mill mode to combine 6. gained agglomerated material is milled to particle size is 2～5 microns powder;
8. remove the impurity that remains in the powder with deionized water and washing with alcohol, in 80～150 ℃ of oven dry 10～30 hours, obtain the powder luminescent material;
9. adopt FluoroMax-4 (HORIBA Jobin Yvon) fluorescence spectrophotometer to measure room temperature excitation spectrum and the emmission spectrum of sample, gather the powder diffraction data of sample with D8 Advance x-ray powder diffraction instrument (Bruker).
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| CN109572271A (en) * | 2017-09-29 | 2019-04-05 | Dx正方有限责任公司 | Printed sheet and preparation method thereof |
| CN112662396A (en) * | 2020-12-29 | 2021-04-16 | 威海市泓淋电力技术股份有限公司 | Solid solution type red long-afterglow luminescent material and preparation method thereof |
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|---|---|---|---|---|
| CN1995277A (en) * | 2006-12-21 | 2007-07-11 | 温州大学 | Single component white light fluorescent powder for LED lamp and its preparation method |
| CN101134895A (en) * | 2006-08-15 | 2008-03-05 | 大连路明科技集团有限公司 | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same |
| CN102071015A (en) * | 2011-01-21 | 2011-05-25 | 中国计量学院 | Europium and manganese co-doped and activated white emitting phosphor and preparation method thereof |
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| CN101134895A (en) * | 2006-08-15 | 2008-03-05 | 大连路明科技集团有限公司 | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same |
| CN1995277A (en) * | 2006-12-21 | 2007-07-11 | 温州大学 | Single component white light fluorescent powder for LED lamp and its preparation method |
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| CN109572271A (en) * | 2017-09-29 | 2019-04-05 | Dx正方有限责任公司 | Printed sheet and preparation method thereof |
| CN112662396A (en) * | 2020-12-29 | 2021-04-16 | 威海市泓淋电力技术股份有限公司 | Solid solution type red long-afterglow luminescent material and preparation method thereof |
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