CN107011900B - Red long-afterglow luminescent material and preparation method thereof - Google Patents
Red long-afterglow luminescent material and preparation method thereof Download PDFInfo
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- 238000001354 calcination Methods 0.000 claims description 19
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- 125000005402 stannate group Chemical group 0.000 abstract description 5
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- 229910052779 Neodymium Inorganic materials 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 2
- 229910052691 Erbium Inorganic materials 0.000 abstract description 2
- 229910052689 Holmium Inorganic materials 0.000 abstract description 2
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 2
- 229910052772 Samarium Inorganic materials 0.000 abstract description 2
- 229910052771 Terbium Inorganic materials 0.000 abstract description 2
- 229910052775 Thulium Inorganic materials 0.000 abstract description 2
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- 239000000203 mixture Substances 0.000 description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 16
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- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 8
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- 150000004645 aluminates Chemical class 0.000 description 2
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 239000012071 phase Substances 0.000 description 2
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- -1 titanates Chemical class 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 1
- 229910002226 La2O2 Inorganic materials 0.000 description 1
- 229910017623 MgSi2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7797—Borates
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- Luminescent Compositions (AREA)
Abstract
The invention discloses a red long afterglow luminescent material, which is characterized by a dual-matrix system with a chemical formula of CaS/CaSnO3Eu, Ln, wherein Ln is one or the combination of more elements of Dy, Tb, Er, Ho, Pr, La, Sm, Ce, Nd, Y, Tm, Yb, Lu and Gd; the invention also discloses a preparation method of the red long-afterglow luminescent material, the red long-afterglow luminescent material prepared by the invention does not need strong light or short wave band (such as ultraviolet) light excitation, can be excited only by common visible light, and the excited material has excellent long-afterglow performance, and the stability of the substrate is obviously improved. Compared with the sulfide matrix long afterglow luminescent material, the chemical stability of the material can be obviously improved, and the defect that the sulfide is easy to deliquesce is particularly improved; compared with stannate substrate long afterglow luminescent materials, the long afterglow luminescent material can expand the wavelength of the excitation light to the visible light range, can be excited by adopting common visible light, and widens the application field of the long afterglow luminescent material.
Description
Technical Field
The invention relates to the field of long-afterglow luminescent materials, in particular to a red long-afterglow luminescent material and a preparation method thereof.
Background
Long Persistent Phosphors (LPPs) are a new type of energy-saving and energy-storing material that can effectively absorb excitation light (such as sunlight) and can continuously emit light for a Long time after the excitation is stopped, and have a wide application prospect in the fields of low-light illumination, emergency indication, architectural decoration, photoelectric elements, biological imaging, clinical medicine, energy and environmental engineering, etc. The existing long afterglow luminescent materials in the visible light region are mainly divided into blue, green and red long afterglow luminescent materials, wherein the blue (such as Sr) is2MgSi2O7:Eu2+,Dy3+Time of afterglow>25h) And green (e.g., SrAl)2O4:Eu2+,Dy3+Time of afterglow>15h) The long afterglow luminance and afterglow time of the long afterglow luminescent material have reached the practical requirement and the commercial application is realized; however, the afterglow luminance and afterglow time of the red long afterglow luminescent material are far inferior to those of the blue and green long afterglow luminescent materials. From the perspective of three primary colors, the long afterglow luminescent materials with the long afterglow colors of red, green and blue are mixed according to a certain proportion to obtain the long afterglow luminescent material with any color, but the three materials are required to have similar chemical properties, afterglow brightness, attenuation rate and the like, otherwise the afterglow color of the mixed material changes in the attenuation process. Therefore, the development delay of the red long-afterglow luminescent material becomes the bottleneck of the full color development process of the long-afterglow luminescent material.
At present, the red long afterglow luminescent material mainly comprises the following matrixes: sulfides, oxysulfides, titanates, silicates, aluminates, and the like. The common preparation method comprises the following steps: high temperature solid phase method, sol-gel method, microwave synthesis method, and the like. In the sulfide long afterglow luminescent material, CaS is Eu2+Is the most studied red long afterglow luminescent material at present, wherein Eu2+Is an activator. Based on the CaS series, the long-afterglow luminescent materials of systems such as (Ca, Sr) S, and (Ca, Mg) S can be obtained by changing the composition of the matrix. However, such materials have the disadvantages of poor chemical stability and deliquescence. The earliest studied in the sulfur oxide system was Y2O2S:Eu2+The system, after which the matrix material gradually expands to (Y, Gd)2O2S、Gd2O2S and La2O2And S and the like. The afterglow brightness of the material is close to the requirement of practical application, but the preparation process conditions of raw material selection, sulfur powder addition form, roasting temperature, sample post-treatment and the like are still required to be perfect, and particularly, the raw material cost is high, so that the further application of the material is hindered. CaTiO in titanate system3:Pr3+The red long afterglow luminescent material is the hotspot of research, CaTiO3The substrate has stable chemical property, good weather resistance and pure luminescent color. However, the greatest disadvantage of this system is insufficient luminance and short afterglow timeIt is required and often requires strong light such as xenon lamp or short-wavelength (e.g. ultraviolet) light to be excited well, so that the excitation intensity in the visible region is still to be improved. In the silicate system there is CdSiO3:Sm3+And MgSiO3:Mn2+,Eu2+,Dy3+The red long-afterglow luminescent materials have good chemical stability and thermal stability, but have the defects of short afterglow time, low brightness and no meeting practical requirements. Sr in aluminate system3Al2O6:Eu2+,Dy3+The material is a red long afterglow material, the luminous brightness and afterglow time are insufficient, and the water resistance is poor. In conclusion, the existing red long afterglow luminescent materials have advantages and disadvantages, and cannot completely meet the requirements of practical application, so that research and development of the red long afterglow luminescent materials with good substrate stability and excellent afterglow performance are particularly necessary.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel red long afterglow luminescent material with good substrate stability and afterglow performance aiming at the defects of the prior art, the luminescent material does not need strong light or short waveband (such as ultraviolet) light excitation, can be excited only by common visible light, the excited material has good long afterglow performance, and the substrate stability is obviously improved.
The invention also provides a preparation method of the red long-afterglow luminescent material.
The technical scheme of the invention is as follows: a red long-afterglow luminescent material features dual-matrix system, whose chemical formula is CaS/CaSnO3Eu, Ln, wherein Ln is one or the combination of more elements of Dy, Tb, Er, Ho, Pr, La, Sm, Ce, Nd, Y, Tm, Yb, Lu and Gd; the doping proportion of Eu ions is CaSnO30.01 mol% -2 mol% of (B), the doping proportion of Ln ions is CaSnO 30 mol% to 1 mol%.
Preferably, the doping ratio of Eu ions is CaSnO30.01 mol% to 1 mol%.
The invention also provides a preparation method of the red long-afterglow luminescent material, which can be called as a wet blending-high temperature solid phase reaction method, and the preparation method comprises the following steps:
a) weighing oxide/carbonate raw materials of corresponding elements according to the stoichiometric ratio of the elements;
b) adding a dispersing agent into the weighed raw materials in the step a), and then carrying out wet blending and grinding;
c) drying the raw materials which are uniformly mixed after the wet blending grinding in the step b);
d) placing the dried raw materials in the step c) in a weak reducing atmosphere for high-temperature solid-phase reaction, wherein the calcining temperature is 900-1350 ℃, and the heat preservation time is 0.5-8 h;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
CaS:Eu2+Belongs to a sulfide system, is the earliest reported red long-afterglow luminescent material, has the advantages of easy excitation, pure luminescent color and the like, but has the defects of poor chemical stability and easy deliquescence. CaSnO3Is a low-dimensional solid luminescent matrix material, and in the stannate structure, the tin element mainly forms stable and firm [ SnO ]6]Octahedral structure, [ SnO6]Different linkage modes of octahedrons can form a low-dimensional crystal structure, particularly a one-dimensional chain structure, CaSnO3Eu as a light emitting ion generating a large number of oxygen vacancies at high temperature2+After doping, due to Eu3+Can change the trap depth and the trap concentration of the matrix so as to effectively trap free carriers, and is used as a storage center to slowly release the free carriers at room temperature to realize long-afterglow emission, however, the reported CaSnO3Most of luminescent materials need strong light such as near ultraviolet to be excited, and are difficult to be excited by common visible light to generate luminescence, so that the application is limited.
The invention successfully synthesizes the dual-matrix long-afterglow luminescent material CaS/CaSnO by accurately adjusting the raw material proportion of oxide or carbonate, controlling the weak reducing atmosphere, the calcining temperature and the heat preservation time3Eu, the double-matrix long-afterglow luminescent material not only has the advantages of easy excitation of sulfide and pure luminescent color, but also has stannate chemistryThe material has the characteristics of good stability and difficult deliquescence, is a novel long-afterglow luminescent material with good substrate stability and excellent long-afterglow performance, and undoubtedly has positive reference significance for the subsequent researches on the substrate stability and afterglow luminescent performance of other related promotion single-substrate luminescent materials.
As a further technical proposal, a fluxing agent, preferably boric acid, can be added in the step a) relative to the matrix CaSnO3Is added in an amount of 0 mol% to 30 mol%, preferably boric acid with respect to the substrate CaSnO3The addition amount of the long afterglow luminescent material is 15mol percent to 25mol percent, which can accelerate the synthesis of the long afterglow luminescent material, reduce the calcination temperature and shorten the heat preservation time.
As a further technical scheme, the dispersing agent in the step b) is absolute ethyl alcohol or water, preferably absolute ethyl alcohol, so that the grinding time can be obviously reduced, the grinding efficiency is improved, and the grinding time is 20-120 min after the dispersing agent is added.
The wet blending-high temperature solid phase reaction method has the advantages that the dispersing agent takes ethanol as an example: in the wet grinding and blending process, on one hand, various required raw materials can be fully dispersed in a liquid dispersion medium, namely ethanol, so that the raw materials are mixed more uniformly. On the other hand, because the wettability of the ethanol is good, an adsorption layer can be formed around the raw material particles, the interface structure of the raw material particles is changed, and the repulsive energy of the interface interaction energy is greater than the attractive energy, so that the raw material particles have good dispersibility and are not easy to agglomerate; meanwhile, due to the wedge crack action of the ethanol molecules in the adsorption layer, the ethanol molecules or molecular groups enter crack gaps or capillaries of the raw material particles to form pinning, so that the structure of the raw material particles is damaged or changed under the action of mechanical grinding to form a new surface, the specific surface area of the raw material particles is increased, and the dispersion degree and the activation degree of the raw material particles are improved; in the subsequent drying process, ethanol molecules volatilize, the raw material particles are more tightly combined due to the action of mechanical stress or capillary force, and the reaction activity is higher in the subsequent high-temperature solid-phase reaction process, so that the double-matrix long-afterglow luminescent material can be synthesized at a lower calcining temperature and in a shorter calcining time.
As a further technical scheme, the drying temperature in the step c) is 60-200 ℃, and the drying time is 1-6 h.
As a further technical scheme, in the step d), the dried raw material may be ground into powder and then put into a high temperature resistant crucible for calcination, or the powder may be pressed into a sheet for calcination.
As a further technical scheme, the formation of the weak reducing atmosphere in the step d) can adopt coal dust as a reducing agent, and on one hand, sulfur in the coal dust is used as a raw material to participate in the synthesis of the dual-matrix luminescent material; on the other hand, carbon in the pulverized coal is used as a reducing agent and is combined with oxygen in the air to form carbon monoxide to produce a weak reducing atmosphere.
As a further technical solution, in the step d), the weak reducing atmosphere is formed by using coal powder as a reducing agent, and sublimed sulfur is added to the raw material or the coal powder as required.
As a further technical solution, the weak reducing atmosphere in step d) may be formed by using activated carbon, and the sublimed sulfur may be introduced in step a) as a source of sulfur in the dual-host luminescent material according to the requirement.
As a further technical solution, the formation of the weak reducing atmosphere in step d) may be to use the reducing gas of the atmosphere furnace to produce the weak reducing atmosphere, such as hydrogen or carbon monoxide, and if necessary, the sublimed sulfur may be introduced in step a) as the source of sulfur in the dual-host luminescent material.
As a further technical scheme, in the step d), when the weak reducing atmosphere is produced by using the reducing gas of the atmosphere furnace, if a mixed gas of carbon monoxide and nitrogen is used, the volume ratio of the carbon monoxide to the nitrogen is 1: 99-20: 80; if a mixed gas of hydrogen and nitrogen is adopted, the volume ratio of the hydrogen to the nitrogen is 1: 99-20: 80.
The beneficial effects obtained by the invention are as follows:
the prior sulfide red long-afterglow luminescent material is easy to be excited by visible light, but has poor chemical stability and easy deliquescence and degeneration in the air, and the stannate red long-afterglow luminescent material has better chemical stability but mostly needs a high-energy light source to be excited, but common visible light is difficult to excite, and the application field is limited; compared with a stannate substrate long-afterglow luminescent material, the double-substrate luminescent material can prolong the wavelength of exciting light to a visible light range, can be excited by adopting common visible light, expands the application field of the double-substrate luminescent material, has good stability, and can meet the requirement of practical application.
The invention provides a preparation method of a double-matrix red long-afterglow luminescent material. The method is called as a wet blending-high temperature solid phase reaction method, and can increase the specific surface area of raw material particles and improve the dispersion degree and the activation degree of the raw material particles; the raw material particles are more tightly combined due to the action of mechanical stress or capillary force in the drying process, and the reaction activity is higher in the subsequent high-temperature solid-phase reaction process, so that the double-matrix long-afterglow luminescent material can be synthesized at a lower calcining temperature and in a shorter calcining time, and the prepared red long-afterglow luminescent material has good crystallinity and afterglow performance. Compared with the traditional high-temperature solid-phase reaction method, the preparation method can further reduce the sample calcination temperature, shorten the heat preservation time and save energy; compared with the existing reported wet chemical method, the preparation method has the advantages of simple and easy process operation, lower cost, suitability for actual production operation and easy popularization.
Drawings
FIG. 1 shows CaS/CaSnO prepared by the present invention30.06% Eu and CaS/CaSnO3XRD spectrum of 0.06 percent of Eu and 0.07 percent of Nd;
FIG. 2 shows CaS/CaSnO prepared by the present invention30.06% Eu;
FIG. 3 shows CaS/CaSnO prepared by the present invention3Excitation spectrum of 0.06% Eu;
FIG. 4 shows CaS/CaSnO prepared by the present invention30.06% Eu in balanceA glow decay curve;
FIG. 5 is a CaS/CaSnO3Deliquescence weight gain curve of 0.06% Eu and CaS, 0.06% Eu;
Detailed Description
The invention will be better understood from the following examples. However, one skilled in the art will readily appreciate that the specific material proportions, process conditions, and results thereof described in the examples are merely illustrative of the invention and should not, nor should they, limit the invention as detailed in the claims.
Example 1:
a) calcium carbonate, tin dioxide and europium oxide were weighed in a stoichiometric molar ratio Ca: Sn: Eu of 2:1:0.01, relative to the substrate CaSnO3Weighing boric acid with the addition amount of 20 mol%;
b) adding water into the mixture obtained in the step a), wherein the water amount is 2 times of the weight of the mixture, and carrying out wet blending and grinding for 1 hour;
c) drying the raw materials which are ground and uniformly mixed in the step b), wherein the drying temperature is 150 ℃, and the drying time is 2 hours;
d) grinding the dried raw materials in the step c) into powder, and performing high-temperature solid-phase reaction in a weak reducing atmosphere by using coal powder as a reducing agent, wherein the calcining temperature is 1300 ℃, and the heat preservation time is 1 h;
e) taking out the calcined sample obtained in the step d) and grinding to obtain the red long-afterglow luminescent material.
Example 2:
a) weighing calcium carbonate, tin dioxide, europium oxide and sublimed sulfur according to the stoichiometric molar ratio of Ca to Sn to Eu to S of 2 to 1 to 0.004 to 0.01;
b) adding water into the mixture obtained in the step a), wherein the water amount is 3 times of the weight of the mixture, and carrying out wet blending and grinding for 2 hours;
c) drying the raw materials which are ground and uniformly mixed in the step b), wherein the drying temperature is 200 ℃, and the drying time is 1 h;
d) grinding the dried raw materials in the step c) into powder, and performing high-temperature solid-phase reaction in a weak reduction atmosphere by using activated carbon as a reducing agent, wherein the calcining temperature is 1350 ℃, and the heat preservation time is 0.5 h;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
Example 3:
a) calcium carbonate, tin dioxide, europium oxide, neodymium oxide and sublimed sulfur were weighed in a stoichiometric molar ratio of Ca to Sn to Eu to Nd to S of 2:1:0.0006:0.0007:0.05, and the resulting mixture was ground to CaSnO3The adding amount of the boric acid is 30mol percent;
b) adding ethanol into the mixture obtained in the step a), wherein the amount of the ethanol is 1 time of the weight of the mixture, and carrying out wet blending and grinding for 2 hours;
c) drying the raw materials which are ground in the step b) and uniformly mixed, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
d) grinding the dried raw materials in the step c) into powder, and preparing a weak reducing atmosphere by using an atmosphere furnace to perform high-temperature solid-phase reaction, wherein the volume ratio of hydrogen to nitrogen is 10:90, the calcining temperature is 900 ℃, and the heat preservation time is 8 hours;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
FIG. 1 shows the co-doping of Eu in this example2+And Nd3+The XRD pattern of the Eu is singly doped with Eu in the same proportion as that of the example 42+XRD pattern of (a). It can be easily found that the phase compositions of the two are basically consistent, and both are CaS and CaSnO3It is demonstrated that the synthesis of the dual substrate of the present invention is successful, only the co-doping of Eu is performed2+And Nd3+Compared with single doped Eu2+The development degree of the CaS crystal phase is relatively improved.
Example 4:
a) calcium carbonate, tin dioxide, europium oxide and sublimed sulphur were weighed in a stoichiometric molar ratio Ca: Sn: Eu: S of 2:1:0.0006:0.05, with respect to the substrate CaSnO3The adding amount of the boric acid is 30mol percent;
b) adding ethanol into the mixture obtained in the step a), wherein the amount of the ethanol is 1 time of the weight of the mixture, and carrying out wet blending and grinding for 2 hours;
c) drying the raw materials which are ground in the step b) and uniformly mixed, wherein the drying temperature is 60 ℃, and the drying time is 6 hours;
d) grinding the dried raw materials in the step c) into powder, and preparing a weak reducing atmosphere by using an atmosphere furnace to perform high-temperature solid-phase reaction, wherein the volume ratio of hydrogen to nitrogen is 10:90, the calcining temperature is 900 ℃, and the heat preservation time is 8 hours;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
FIG. 2 shows the CaS/CaSnO prepared in this example30.06% Eu, excitation wavelength of 439nm, and the emission peak of the composite host luminescent material prepared in this example is near 640nm, which is considered to be red light emission. FIG. 3 shows the CaS/CaSnO prepared in this example30.06% Eu, and the monitored wavelength is 640nm, and the excitation peak of the sample shows a wide excitation peak in a visible wave band of 400-600 nm, which shows that the sample can be excited by visible light.
FIG. 4 shows the CaS/CaSnO prepared in this example30.06% Eu, initial afterglow intensity close to 400mcd/m2The afterglow time reaches 48 min.
FIG. 5 shows the CaS/CaSnO prepared in this example30.06% Eu and 0.06% Eu, which is the same as CaS, other raw materials and preparation conditions. From the figure, the deliquescence trends of the two luminescent materials are steadily increased, the deliquescence stability of the composite matrix system is superior to that of the single-matrix sulfide system, the former is increased by 0.0136 percent and the latter is increased by 0.023 percent and the CaS/CaSnO is increased by 0.023 percent after 96 hours3The weight gain of 0.06% Eu is only 59% of that of 0.06% Eu in CaS.
Example 5:
a) calcium carbonate, tin dioxide, europium oxide and sublimed sulfur were weighed in a stoichiometric molar ratio of Ca: Sn: Eu: S of 2:1:0.02:0.1, with respect to the substrate CaSnO3Weighing boric acid with the addition amount of 15 mol%;
b) adding ethanol into the mixture obtained in the step a), wherein the amount of the ethanol is 1 time of the weight of the mixture, and carrying out wet blending and grinding for 20 min;
c) drying the raw materials which are ground and uniformly mixed in the step b), wherein the drying temperature is 100 ℃, and the drying time is 3 hours;
d) grinding the dried raw materials in the step c) into powder, and preparing a weak reducing atmosphere by using an atmosphere furnace to perform high-temperature solid-phase reaction, wherein the volume ratio of carbon monoxide to nitrogen is 20:80, the calcining temperature is 1200 ℃, and the heat preservation time is 3 hours;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
Example 6:
a) calcium carbonate, tin dioxide and europium oxide were weighed in a stoichiometric molar ratio Ca: Sn: Eu of 2:1:0.0001, with respect to the substrate CaSnO3Weighing boric acid with the addition amount of 10 mol%;
b) adding ethanol into the mixture obtained in the step a), wherein the amount of the ethanol is 1 time of the weight of the mixture, and carrying out wet blending and grinding for 20 min;
c) drying the raw materials which are ground in the step b) and uniformly mixed, wherein the drying temperature is 80 ℃, and the drying time is 5 hours;
d) grinding the dried raw materials in the step c) into powder, and performing high-temperature solid-phase reaction in a weak reducing atmosphere by using coal powder as a reducing agent, wherein the calcining temperature is 1250 ℃, and the heat preservation time is 2 hours;
e) taking out the calcined sample obtained in the step d) and grinding to obtain the red long-afterglow luminescent material.
Example 7:
a) calcium carbonate, tin dioxide, europium oxide and sublimed sulfur were weighed in a stoichiometric molar ratio of Ca: Sn: Eu: S of 2:1:0.008:0.2, with respect to the substrate CaSnO3Weighing boric acid with the addition amount of 23 mol%;
b) adding ethanol into the mixture obtained in the step a), wherein the amount of the ethanol is 1.5 times of the weight of the mixture, and carrying out wet blending and grinding for 1.5 hours;
c) drying the raw materials which are ground in the step b) and uniformly mixed, wherein the drying temperature is 120 ℃, and the drying time is 2.5 hours;
d) grinding the dried raw materials in the step c) into powder, and preparing a weak reducing atmosphere by using an atmosphere furnace to perform high-temperature solid-phase reaction, wherein the volume ratio of hydrogen to nitrogen is 1:99, the calcining temperature is 1280 ℃, and the heat preservation time is 4 hours;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
Example 8:
a) in stoichiometric molar ratioCa Sn Eu 2:1:0.015 calcium carbonate, tin dioxide and europium oxide were weighed out in a proportion of CaSnO matrix3The adding amount of the boric acid is 5mol percent;
b) adding water into the mixture obtained in the step a), wherein the water amount is 2 times of the weight of the mixture, and carrying out wet blending and grinding for 120 min;
c) drying the raw materials which are ground in the step b) and uniformly mixed, wherein the drying temperature is 150 ℃, and the drying time is 3 hours;
d) grinding the dried raw materials in the step c) into powder, taking coal powder as a reducing agent, adding sublimed sulfur accounting for 5 percent of the weight of the coal powder into the coal powder, and carrying out high-temperature solid-phase reaction in a weak reducing atmosphere, wherein the calcining temperature is 1250 ℃, and the heat preservation time is 2 hours;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
Claims (17)
1. A red long-afterglow luminescent material features dual-matrix system, whose chemical formula is CaS/CaSnO3Eu and Ln, wherein Ln is Nd; the doping proportion of Eu ions is CaSnO30.01 mol% -2 mol% of (B), the doping proportion of Ln ions is CaSnO30 mol% to 1 mol%.
2. The red long-afterglow luminescent material of claim 1, wherein the doping ratio of Eu ions is CaSnO30.01 mol% to 1 mol%.
3. The preparation method of the red long-afterglow luminescent material as claimed in claim 1, which is a wet blending-high temperature solid phase reaction method, comprising the following steps:
a) weighing oxide/carbonate raw materials of corresponding elements according to the stoichiometric ratio of the elements;
b) adding a dispersing agent into the weighed raw materials in the step a), and then carrying out wet blending and grinding;
c) drying the raw materials which are uniformly mixed after the wet blending grinding in the step b);
d) placing the dried raw materials in the step c) in a weak reducing atmosphere for high-temperature solid-phase reaction, wherein the calcining temperature is 900-1350 ℃, and the heat preservation time is 0.5-8 h;
e) taking out the calcined sample in the step d) and grinding to obtain the red long afterglow luminescent material.
4. The method for preparing a red long-afterglow luminescent material of claim 3, wherein a flux is added in the step a).
5. The method for preparing a red long-afterglow luminescent material as claimed in claim 4, wherein the fluxing agent is boric acid.
6. The method for preparing red long-afterglow luminescent material of claim 5, wherein the boric acid is relative to the substrate CaSnO3The addition amount of (A) is 15 mol% -25 mol%.
7. The method for preparing a red long-afterglow luminescent material of claim 3, wherein the dispersant in the step b) is absolute ethyl alcohol or water.
8. The method for preparing a red long-afterglow luminescent material as claimed in claim 7, wherein the dispersant is absolute ethyl alcohol.
9. The method for preparing a red long-afterglow luminescent material as claimed in claim 7, wherein the grinding time is 20 to 120min after the dispersant is added.
10. The method for preparing a red long-afterglow luminescent material as claimed in claim 3, wherein the drying temperature in step c) is 60 to 200 ℃ and the drying time is 1 to 6 hours.
11. The method for preparing a red long-lasting phosphor according to claim 3, wherein the dried raw material is pulverized into powder and then charged into a high temperature crucible for firing or pressed into a sheet for firing in the step d).
12. The method for preparing a red long-afterglow luminescent material as claimed in claim 3, wherein the formation of the weak reducing atmosphere in the step d) uses pulverized coal as a reducing agent.
13. The method for preparing red long-afterglow luminescent material of claim 12, wherein sublimed sulfur is added to the raw material or pulverized coal when pulverized coal is used as a reducing agent.
14. The method for preparing a red long-afterglow luminescent material as claimed in claim 3, wherein the formation of the weakly reducing atmosphere in step d) is performed by using activated carbon to prepare the weakly reducing atmosphere, and the sublimed sulfur is introduced in step a) as a source of sulfur in the dual-matrix luminescent material.
15. The method for preparing a red long-afterglow luminescent material of claim 3, wherein the formation of the weak reducing atmosphere in the step d) adopts an atmosphere of introducing a reducing gas, and sublimed sulfur is introduced in the step a) as a source of sulfur in the dual-matrix luminescent material.
16. The method for preparing a red long-afterglow luminescent material as claimed in claim 15, wherein the reducing gas is a mixed gas of hydrogen and nitrogen, wherein the volume ratio of hydrogen to nitrogen is 1: 99-20: 80.
17. The method for preparing a red long-afterglow luminescent material as claimed in claim 15, wherein the reducing gas is a mixed gas of carbon monoxide and nitrogen, wherein the volume ratio of carbon monoxide to nitrogen is 1: 99-20: 80.
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| US6686691B1 (en) * | 1999-09-27 | 2004-02-03 | Lumileds Lighting, U.S., Llc | Tri-color, white light LED lamps |
| CN101696354A (en) * | 2009-10-26 | 2010-04-21 | 井冈山大学 | Method for preparing europium-doped calcium stannate luminescent material |
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