CN103059840B - 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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- CN103059840B CN103059840B CN201210428918.7A CN201210428918A CN103059840B CN 103059840 B CN103059840 B CN 103059840B CN 201210428918 A CN201210428918 A CN 201210428918A CN 103059840 B CN103059840 B CN 103059840B
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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 the White ultra-long afterglow luminescent material and preparation method thereof of a kind of near ultraviolet and excited by visible light.
Background technology
Fluorophor refers to outside stimulus effects such as utilizing particle energy, electronics, light, carries out exciting and a kind of functional material of luminescence, and still the illuminator of continuous illumination can be called " luminous storage material ", i.e. long after glow luminous material by after exciting stopping.Such luminescent material require in practical multicolor and afterglow property excellent, good weatherability.
Hitherto known long after glow luminous material, on matrix of materials composition, kind is few, and is generally all subject to restriction that the is luminous and shortcomings such as twilight sunset Energy distribution is narrower, color is dull and persistence is short, and weatherability is poor.
For phosphor, be first sulfide-based fluorophor, such as, (Ca, Sr) S:Bi in blue-light-emitting
3+the ZnS:Cu of fluorophor, yellow green luminescence
2+(Zn, Cd) S:Cu fluorophor etc. of fluorophor, emitting red light, maximum shortcoming with regard to less stable, illuminator brightness and the twilight sunset life-span also insufficient.In addition, (Zn, Cd) S: Cu fluorophor contain toxicant cadmium, use restricted especially.ZnS:Cu
2+fluorophor, in humid conditions, easily decomposes and blackening by Ultraviolet radiation, and persistence is also insufficient, and the clock and watch word dish used as cheapness and refuge guide mark etc., also can only be used for indoor.Oxysalt system fluorophor, such as europkium-activated alkali earth metal aluminate MAl
2o
4(here M be magnesium, calcium, strontium, barium one or several), although have as Journal of Electrochemical Society, the 118th volume, the SrAl that 930 pages (1971) report
2o
4: more long-life long afterglow performance of Eu fluorophor display, but, owing to being easy to deliquescence, as luminous storage material Practical Performance or not ideal enough.Silicate fluorophor is as growing remaining luminescent material, the problem that ubiquity afterglow property is undesirable.On the other hand, only near 520nm/500nm, have maximum emission intensity using europium as the strontium of dominant activator aluminate/barium aluminate salt, luminous in yellow green, brightness decay is to 0.32mcd/m
2time more than 2000 minutes, compared with 200 minutes of ZnS:Cu fluorophor, light-decay characteristic is more excellent, but it still has the shortcomings such as the dull and weatherability of glow color is poor.
Summary of the invention
The object of the present invention is to provide a kind of have white luminous, long afterglow performance is good, the stuctures and properties of material is to the White ultra-long afterglow luminescent material of heat and the advantage such as chemical environment is stablized, weatherability is excellent.
Another object of the present invention is to provide its preparation method of above-mentioned White ultra-long afterglow luminescent material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of White ultra-long 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 above formula
*be expressed as the metallic element of more than a kind or a kind that selects from magnesium, calcium, strontium, barium and zinc,
a, b, x, ybe amount of substance, meet 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 by europium and manganese codoped or, europium, manganese and more than a kind and a kind other rare earth elements RE codope or the white luminous luminous storage material activated with other ion generation energy transferring.
A kind of White ultra-long 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 above formula
*be expressed as the metallic element of more than a kind or a kind that selects from magnesium, calcium, strontium, barium and zinc, RE represents more than a kind or a kind in rare-earth element cerium, praseodymium, neodymium, samarium, dysprosium, holmium, ytterbium,
a, b, x, k, ybe amount of substance, meet 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。
In order to ensure the luminescent properties that luminous storage material of the present invention is good and chemistry, heat endurance and weatherability, first determine the ratio of aluminium and silicon, the composition of aluminium and silicon should meet: 0.5≤(
a+
b)≤5,
b=(0.1 ~ 10)
a; If the M element be in this constituent is with M such as a part of zinc
*element replaces, then luminous storage material long afterglow performance is deteriorated to some extent, but improves luminosity and whiteness.
Determine to be included in the above-mentioned of the europium composition in aluminium silicon salt long after glow luminous material of the present invention
xvalue, suitable scope is 0.001≤
x≤ 0.1.The ionic weight becoming the centre of luminescence is few, can not get good luminosity, if
xvalue, more than 0.1, while causing with concentration delustring between luminescent center ion, or produces the compound beyond target, or the oxide of remaining raw material, and the brightness of luminous storage material also can significantly reduce, i.e. concentration quenching.
Determine to be included in the above-mentioned of the manganese composition in aluminium silicon salt long after glow luminous material of the present invention
yvalue, suitable scope is 0.001≤
y≤ 0.5.The ionic weight becoming the centre of luminescence is few, can not get good white-light emitting, if
yvalue, more than 0.5, while causing with concentration delustring between luminescent center ion, or produces the compound beyond target, or the oxide of remaining raw material, or luminous storage material powder colour-darkening, and the brightness of luminous storage material also can significantly reduce, i.e. concentration quenching.
Use the rare earth element such as cerium, praseodymium, neodymium, samarium, dysprosium, holmium, ytterbium and europium together with manganese as co-dopant time, above-mentioned
kthe scope that value should meet is 0.1≤
k:
x≤ 3, luminous storage material has maximum luminosity, and long afterglow performance also improves.
A kind of preparation method of described White ultra-long afterglow luminescent material, the method is burnt till together with flux by material powder, firing condition is: under reducing atmosphere in 900 ~ 1400 DEG C of thermostatic 2 ~ 4 hours, after cooling after pulverizing grinding briquet, under reducing atmosphere in 1100 ~ 1400 DEG C of thermostatic 3 ~ 8 hours, pulverize after sintered body cooling, washing, dry, grinding, the Powdered product of gained is described White ultra-long afterglow luminescent material;
Described material powder is by the compound containing M element, containing M
*the ratio that the compound of element, the compound containing Al element, the compound containing Si element, the compound containing Eu element, compound containing Mn element represent with general formula (1) mixes.
As preferably, described material powder is selected from M or M
*or the carbonate of Mn element or subcarbonate or oxide, aluminium oxide or aluminium hydroxide, SiO 2 powder or metasilicic acid or orthosilicic acid, europium oxide or europium carbonate or oxalic acid europium.
As preferably, described cosolvent be boric acid or boron oxide time, consumption is the 3-4% of material powder weight; Described cosolvent be ammonium halide salt or, when alkali-metal carbonate or fluoride, consumption is the 4-5% of material powder weight.
As preferably, described Powdered product particle diameter is 2 ~ 5 μm.
As preferably, the cleaning solution adopted in 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 gaseous mixture of wherein one or several and nitrogen or argon gas, or is provided by activated carbon powder combustion method.
A kind of preparation method of described White ultra-long afterglow luminescent material, the method is burnt till together with flux by material powder, firing condition is: under reducing atmosphere in 900 ~ 1400 DEG C of thermostatic 2 ~ 4 hours, after cooling after pulverizing grinding briquet, under reducing atmosphere in 1100 ~ 1400 DEG C of thermostatic 3 ~ 8 hours, pulverize after sintered body cooling, washing, dry, grinding, the Powdered product of gained is described White ultra-long afterglow luminescent material;
Described material powder is by the compound containing M element, containing M
*the compound of element, the compound containing Al element, the compound containing Si element, the compound containing Eu element, compound containing Mn element and, the ratio that the compound containing more than a kind or a kind rare earth elements RE represents with general formula (2) mixes.
As preferably, the method specifically comprises the steps:
1. the material powder described in White ultra-long afterglow luminescent material is selected from M or M
*or the carbonate of Mn element or subcarbonate or oxide, aluminium oxide or aluminium hydroxide, SiO 2 powder or metasilicic acid or orthosilicic acid, europium oxide or europium carbonate or oxalic acid europium, rare-earth oxide;
2. adopting planetary ball mill to be carried out by the raw material of load weighted aluminium, silicon and europium being milled to particle diameter is 2 ~ 5 μm;
3. the aluminium after ball milling, silicon are carried out abundant ball milling with the raw material of europium together with load weighted calcium, magnesium, strontium, barium, zinc, manganese and other rare earths material and flux, Ball-milling Time is 10 ~ 25 hours;
4. adopt metal die on a hydraulic press sufficient for grinding dusty material pressure knot to be obtained biscuit with two-way press moulding mode, pressure knot pressure is 1000 ~ 5000kg/cm
2;
5. biscuit is put into corundum crucible, with high temperature resistance furnace, under the reducing condition of active carbon or hydrogen, with the heating rate of 100 ~ 300 DEG C/h to 900 ~ 1400 DEG C, and be incubated 2 ~ 4 hours, drop to room temperature with the rate of temperature fall of 2 ~ 10 DEG C/min subsequently, obtain agglomerated material;
6. the agglomerated material of 5. gained is ground 1 hour by hand, 4. biscuit is obtained again by step, put into corundum crucible, with high temperature resistance furnace, under activated carbon grain or hydrogen reducing condition, be heated to 1100 ~ 1400 DEG C with the speed of 200 ~ 500 DEG C/h, constant temperature 3 ~ 8 hours, be cooled to room temperature with the speed of 2 ~ 10 DEG C/min subsequently, obtain agglomerated material;
7. adopt hand lapping and planetary ball mill mode to combine and 6. gained agglomerated material is milled to the powder that particle size is 2 ~ 5 microns;
8. remove with deionized water and ethanol washing the impurity remained in powder, dry 10 ~ 30 hours in 80 ~ 150 DEG C, obtain powder luminescent material;
9. adopt FluoroMax-4 (HORIBA Jobin Yvon) XRF to measure room temperature excitation spectrum and the emission 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 ultra-long 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 carry out exciting with electron beam or ultraviolet or visible ray or their combination and produce white luminous, after exciting stopping, still there is white long afterglow luminescent properties, and heat, chemical stability are good, aluminosilicate White ultra-long afterglow luminescent material being co-dopant with rare earth element and manganese and preparation method thereof.
In order to achieve the above object, the present inventor take aluminosilicate as matrix, new composition new construction illuminator is studied, obtain the reaction product of the aluminosilicate containing specific composition, carry out adulterating with europium and manganese and europium and other ion generation energy transferring or and other rare earth elements RE carry out codope, prepare the aluminosilicate series long afterglow luminescent material made new advances.
The present invention has successfully prepared the aluminosilicate White ultra-long afterglow luminescent material of a kind of novel europium and manganese and other rare earth element codope by selecting the collocation of suitable aluminosilicate matrix material, adulterant, flux and preparation technology.
In order to obtain having the luminous aluminosilicate luminous storage material of certain particle diameter (2 ~ 5 μm) powdery white, if using boric acid or boron oxide as flux, can there is solid solution with a part of Al and replace in boron, long afterglow improves, but its substitution amount should not be excessive.Superfluous boron component, contributes to glassy phase and generates, be unfavorable for luminosity and residual photosensitiveness.If using ammonium halide salt or alkali-metal carbonate or fluoride as flux, should control the amount of flux, too much flux can make luminous storage material excess agglomeration, affects luminosity and residual photosensitiveness.
Aluminosilicate luminous storage material of the present invention is after utilizing the ultraviolet of electron beam or 250 ~ 430nm scope or visible ray or their several combined dopants, more than room temperature or room temperature, and the luminescent material of display twilight sunset (fluorescence).
The primary raw material of this long after glow luminous material is, the compound containing M element, containing M
*the compound of element, the compound containing aluminium element, the compound containing element silicon, the compound containing europium element, compound containing manganese element and the compound containing rare earth elements RE, namely containing the oxide of these elements or the hydrate of hydroxide or oxide or oxalates or carbonate or nitrate or sulfate etc.The composition they being pressed above-mentioned (1) or (2) formula weighs, and fully mixes, is placed in the heat-resisting reaction vessel such as alumina crucible or graphite crucible.The powder diffraction pattern (XRD) of luminescent material of the present invention is shown in Fig. 1.The present invention passes through the suitable compatibility of centre of luminescence europium or manganese and rare earth elements RE and some other element, as occur between europium energy transferring ion, form the ion of trap level, the element kind such as boron, sodium, lithium of the promotion particle growth be included in flux and the optimization of content thereof, obtain having that the afterglow property of overlength, structural chemistry good stability, weatherability are excellent, emission spectrum Energy distribution at 400 ~ 650nm, peak value is positioned at the white luminescent material (see figure 2) of 436nm and 561nm.
Sintered body structure is loose, and be easy to broken, powder particle size about 2 ~ 5 μm, has fine weatherability and acid-alkali-corrosive-resisting, and twilight sunset is in white, and persistence was more than 12 hours.
Accompanying drawing explanation
Fig. 1 is the powder diffraction pattern (XRD) of luminescent material of the present invention;
Fig. 2 is the excitation spectrum that records of luminescent material ultraviolet courseware spectrophotometer of the present invention and emission spectrum.
Detailed description of the invention
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 make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is conventional.
Embodiment 1:
A kind of White ultra-long 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, M* is Mg, a=1.0, b=1.0, x=0.05, y=0.4.
Preparation method is as follows:
Take 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.Boric acid consumption is 3.5% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and CaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1300 DEG C of constant temperature 2 hours are heated to the speed of 500 DEG C/h, be cooled to room temperature with the speed of 2 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1200 DEG C of constant temperature 8 hours are heated to the speed of 350 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 2:
A kind of White ultra-long 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, M* is Ba, a=1.0, b=2.0, x=0.05, y=0.2.
Preparation method is as follows:
Take material powder: CaCO
30.35mol, BaCO
30.4mol, Eu
2o
30.05mol, MnCO
30.2mol, Al2O
3micro mist 1mol, SiO
2fine powder 2mol.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3carrying out being milled to particle diameter is 3 microns, subsequently by the oxide mixed-powder that obtains and CaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 3 hours are heated to the speed of 200 DEG C/h, be cooled to room temperature with the speed of 5 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1250 DEG C of constant temperature 6 hours are heated to the speed of 450 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 5 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 3:
A kind of White ultra-long 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, M* is Zn, a=1.0, b=0.5, x=0.005, y=0.2.
Preparation method is as follows:
Take material powder: SrCO
30.395mol, ZnCO
30.4mol, Eu
2o
30.005mol, MnCO
30.2mol, Al2O
3micro mist 1mol, SiO
2fine powder 0.5mol.Boric acid consumption is 3% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3carrying out being milled to particle diameter is 5 microns, subsequently by the oxide mixed-powder that obtains and SrCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1050 DEG C of constant temperature 4 hours are heated to the speed of 100 DEG C/h, be cooled to room temperature with the speed of 10 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1200 DEG C of constant temperature 8 hours are heated to the speed of 450 DEG C/h, room temperature is cooled to subsequently with the speed of 5 DEG C/min, obtain sintered material, it is 4 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 4:
A kind of White ultra-long 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, M* is Zn, a=0.5, b=1, x=0.002, y=0.05.
Preparation method is as follows:
Take 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.Boric acid consumption is 3% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and (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 3500kg/cm
2pressure be pressed into the biscuit that diameter is 13mm, then this biscuit is put into corundum crucible, with high temperature resistance furnace, under hydrogen reducing condition, 950 DEG C of constant temperature 2 hours are heated to the speed of 200 DEG C/h, be cooled to room temperature with the speed of 2 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1300 DEG C of constant temperature 4 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 5:
A kind of White ultra-long 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, M* be Zn, Re is Ce, a=2.5, b=2.0, x=0.02, k=0.03, y=0.15.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Ce
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and CaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 950 DEG C of constant temperature 3 hours are heated to the speed of 200 DEG C/h, be cooled to room temperature with the speed of 8 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1280 DEG C of constant temperature 4 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 6:
A kind of White ultra-long 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, M* be Zn, Re is Dy, a=1.0, b=2.5, x=0.03, k=0.04, y=0.05.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Dy
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and BaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 4 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 10 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1300 DEG C of constant temperature 5 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 4 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 7:
A kind of White ultra-long 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, M* be Zn, Re is Nd, a=1.5, b=3.0, x=0.01, k=0.03, y=0.20.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Nd
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and SrCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 4 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 10 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1300 DEG C of constant temperature 5 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 4 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 8:
A kind of White ultra-long 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, M* be Mg, Re is Nd+Pr, a=1.0, b=4.0, x=0.03, k=0.04, y=0.20.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Nd
2o
3, Pr
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and CaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 900 DEG C of constant temperature 3 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 5 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1350 DEG C of constant temperature 3 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 8 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 9:
A kind of White ultra-long 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, M* be Mg, Re is Dy+Ce, a=2.0, b=3.0, x=0.04, k=0.04, y=0.30.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Dy
2o
3, Ce
2o
3carrying out being milled to particle diameter is 4 microns, subsequently by the oxide mixed-powder that obtains and BaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1100 DEG C of constant temperature 2 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 5 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1400 DEG C of constant temperature 2 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 10:
A kind of White ultra-long 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, M* be Mg, Re is Dy+Nd, a=1.0, b=3.0, x=0.02, k=0.04, y=0.10.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Dy
2o
3, Ce
2o
3carrying out being milled to particle diameter is 4 microns, subsequently by the oxide mixed-powder that obtains and SrCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 3 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 8 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1200 DEG C of constant temperature 8 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Embodiment 11:
A kind of White ultra-long 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, M* be Zn, Re is Dy+Ce, a=2.0, b=2.0, x=0.02, k=0.03, y=0.10.
Preparation method is as follows:
Take 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.Boric acid consumption is 4% of material powder gross weight.Adopt planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Dy
2o
3, Ce
2o
3carrying out being milled to particle diameter is 4 microns, subsequently by the oxide mixed-powder that obtains and CaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 3 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 8 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1200 DEG C of constant temperature 8 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 3 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 (HORIBA Jobin Yvon) XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument (Bruker.).
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (2)
1. a White ultra-long afterglow luminescent material, is characterized in that: 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, M* be Zn, Re is Dy, a=1.0, b=2.5, x=0.03, k=0.04, y=0.05; The preparation method of this luminescent material is as follows:
Take 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, boric acid consumption is 4% of material powder gross weight, adopts planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Dy
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and BaCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 4 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 10 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1300 DEG C of constant temperature 5 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 4 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument.
2. a White ultra-long afterglow luminescent material, is characterized in that: 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, M* be Zn, Re is Nd, a=1.5, b=3.0, x=0.01, k=0.03, y=0.20, and preparation method is as follows:
Take 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, boric acid consumption is 4% of material powder gross weight, adopts planetary ball mill by Al
2o
3, SiO
2, Eu
2o
3, Nd
2o
3carrying out being milled to particle diameter is 2 microns, subsequently by the oxide mixed-powder that obtains and SrCO
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, with high temperature resistance furnace, under hydrogen reducing condition, 1000 DEG C of constant temperature 4 hours are heated to the speed of 300 DEG C/h, be cooled to room temperature with the speed of 10 DEG C/min subsequently, grind 1 hour by hand, then 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, with high temperature resistance furnace, under active carbon granule reducing condition, 1300 DEG C of constant temperature 5 hours are heated to the speed of 400 DEG C/h, room temperature is cooled to subsequently with the speed of 10 DEG C/min, obtain sintered material, it is 4 μm that sintered body is milled to average particle size particle size by the mode adopting hand lapping and planetary type ball-milling to combine, with deionized water and ethanol washing removing residual impurity, dry 24 hours in 115 DEG C, the obtained uniform luminescent material powder of Granular composite, room temperature excitation spectrum and the emission spectrum of sample is measured with FluoroMax-4 XRF, the powder diffraction data of sample is gathered with D8 Advance x-ray powder diffraction instrument.
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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 |
| 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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