CN105368448A - Alkaline earth metal silicate yellow-orange fluorescent powder and preparation method therefor and application thereof - Google Patents
Alkaline earth metal silicate yellow-orange fluorescent powder and preparation method therefor and application thereof Download PDFInfo
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Abstract
The present invention discloses alkaline earth metal silicate yellowish-orange fluorescent powder, wherein the chemical formula thereof is SrxAySiO5:Euz, Dm. In the formula, A is at least one of Ba, Ca and Mg, and D is one of Sc, Y, La and Lu, wherein x is greater than or equal to 2.2 but less than 3, y is greater than or equal to 0 but less than or equal to 0.7, z is greater than or equal to 0.005 but less than or equal to 0.1, m is greater than or equal to 0.005 but less than or equal to 0.1, and x+y+z=3. The preparation method comprises: weighting oxides and carbonates of the elements according to the molar ratio in the chemical formula; mixing and grinding the oxides and the carbonates; carrying a temperature reaction under a reduction atmosphere; performing cooling; performing grinding; performing sieving; performing acid pickling; and performing drying. The fluorescent powder provided by the present invention broadens the emission spectrum, and increases the half peak width; the center wavelength thereof can shift between 571 nm and 612 nm, the fluorescent powder is small in particle size, uniform in distribution, good in crystallization and suitable for being widely used in high color rendering illumination and backlight field thereof. The preparation method is simple and easy to handle, the sinter temperature required by the preparation process is relatively low, and the process window is wide, so that the preparation method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to luminescent material and its production and use, specifically a kind of alkaline earth metal silicate Huang-orange fluorescent powder and its preparation method and application.
Background technology
Rare earth luminescent material has become the propping material in the fields such as information displaying, lighting source, photoelectric device in recent years, the high luminous intensity of fluorescent material and good microscopic appearance can improve the use properties of luminescent device effectively, therefore, the investigation and application of novel fluorescent material is one of important research field of materials chemistry and materials physics always.
White light emitting diode (Whitelight-emittingdiode, WLED) shortcomings such as many, the frangible and gurry mercury pollution of power consumption that conventional incandescent and luminescent lamp exist not only are overcome, also have volume little, can low pressure or low current start, the life-span is long, the resistance to punching of antidetonation, recyclable, can the features such as planar package, ecnomics and enviroment benefit be obvious, become one of rival the strongest in illuminating industry.
At present, the method that in industry, technology is comparatively ripe adopts InGaN blue chip coating YAG:Ce yellow fluorescent powder to form white light LEDs.Although wherein adopted YAG:Ce yellow fluorescent powder has the advantage such as high-luminous-efficiency, emission spectrum bandwidth, but, but have that colour rendering index is low in actual use, the shortcomings such as red color light component is not enough in spectrum, cause it to be difficult to obtain the white light LED part compared with high color rendering index (CRI), be also difficult to realize warm white.Therefore, be necessary very much to develop the Huang-orange light emitting materials having certain red color light component that efficiently can be excited by blue light.
Be that the luminescent material of matrix is owing to having good chemical stability, thermostability, wider excitation spectrum, by ultraviolet, near-ultraviolet ray, the blue-light excited light sending shades of colour, can become the important luminescent material of the widely used class of current white light LEDs with silicate.As US7045826 discloses a kind of europium doped silicate fluorescent material Sr
3siO
5: Eu
2+, it is a kind of orange light emitting materials that can be excited within the scope of wavelength 350 ~ 470nm, can make up the shortcoming of YAG in use ruddiness composition deficiency, obtains warm white LED; But, in actual production process, find Sr
3siO
5: Eu
2+fluorescent material peak width at half height is narrower, and after lamp processed, color developing is poor, and in addition, the granularity of its fluorescent material prepared is generally bigger than normal, and particle surface after fragmentation is mellow and full not, and then affects light-out effect.And for example, EP20050823132 discloses a kind of general formula is (Sr, A
1)
x(Si, A
2) (O, A
3)
2+x: Eu
2+silicate-based orange fluorescent material, wherein A
1be positive divalent cation, comprise at least one in Mg, Ca, Ba; A
2be+3 ,+4 or+5 positively charged ions, comprise at least one in B, Al, Ga, C, Ge, P; A
3be-1 ,-2 or-3 negatively charged ion, comprise F, Cl and Br, take preferably F as fusing assistant, synthetic method is coprecipitation method, to reach the object improving light efficiency.But coprecipitation method step is various, more complicated, and fluorine-containing liquid waste disposal is difficult, easily causes environmental pollution.For another example, Chinese patent CN102286282B discloses a kind of general formula is Sr
2-x-y-zlu
yba
zsiO
4: xEu
2+silicate yellow orange fluorescent powder, in formula, x is the mole number of europium atom, and y is the mole number of lutetium atom, and z is the mole number of barium atom, 0.005≤x≤0.15,0.01≤y≤0.15,0≤z≤1.5.The emission center wavelength of fluorescent material is between 515 ~ 570nm, and spectrum that is yellow with routine, orange and orange fluorescent powder is consistent, can be used for the coating of multiple color temperatures white light LEDs, and makes up the deficiency that YAG yellow fluorescent powder in use lacks ruddiness.But from emmission spectrum scope, Sr
2-x-y-zlu
yba
zsiO
4: xEu
2+the orange-colored light that silicate fluorescent powder is launched is pure not, and raw material Lu
2o
3expensive, although particle is less in its SEM figure, granule-morphology crystallinity is poor, do not disperse, have agglomeration.As can be seen here, although the orange fluorescent powder prepared with silicate doping with rare-earth ions in existing technology can be effectively luminous, realize warm white LED, but its preparation method is complicated, and cost is higher, and its peak width at half height relative narrower, luminous intensity is poor, color developing is poor, and particle diameter is large and distribute wide, easy occurrence temperature quencher.Therefore, how new matrix is stablized, synthesis condition is simple, cost is low and peak width at half height is relatively wider, crystalline phase is good, particle diameter is large and Huang-the orange fluorescent powder of the excellent combination property such as narrowly distributing, good luminous performance is the problem of active research always in industry in exploitation.
Summary of the invention
The object of this invention is to provide a kind of alkaline earth metal silicate Huang-orange fluorescent powder and its preparation method and application, to solve the large and problem of the integrated application poor-performings such as distribute wide, peak width at half height is narrower, luminescent properties is poor and cost is high, complicated process of preparation of existing orange fluorescent powder particle diameter.
The object of the invention is to be achieved through the following technical solutions: a kind of alkaline earth metal silicate Huang-orange fluorescent powder, the chemical general formula of this fluorescent material is Sr
xa
ysiO
5: Eu
z, D
m; In formula, A is at least one in Ba, Ca and Mg, and D is the one in Sc, Y, La, Lu; And 2.2≤x < 3,0≤y≤0.7,0.005≤z≤0.05,0.005≤m≤0.1, x+y+z=3; The mole number of fusing assistant is the 0.01-0.1 of Si in matrix.
Preferably, 2.28≤x≤2.9 in chemical general formula, 0.005≤y≤0.5,0.01≤z≤0.04,0.01≤m≤0.08 and x+y+z=3.And under optimum condition, it is good that prepared fluorescent material has grain diameter controllability, and half-peak is wide, the adjustable advantage of peak wavelength.The mole number of fusing assistant is the 0.02-0.09 of Si in matrix.
More preferably, 2.4≤x≤2.9 in chemical general formula, 0.005≤y≤0.25,0.01≤z≤0.03,0.03≤m≤0.06 and x+y+z=3.The mole number of fusing assistant is the 0.04-0.08 of Si in matrix.Under still more preferential conditions, prepared fluorescent material has work in-process small-particle even particle size distribution, and luminous intensity is large.Its Main Function of alkaline-earth metal Ba, Ca, Mg regulates the position of centre wavelength and the width of peak width at half height, and when the mole number of y is in preferred scope, fluorescent material product obtains excellent color display; Within the scope of the preferred molar number z of europium, effectively can play the function of activator, its luminous intensity is better.And when m and fusing assistant are in preferable range, product cut size can be controlled well near 10 μm, and overall target is better.
Present invention also offers the preparation method of a kind of alkaline earth metal silicate Huang-orange fluorescent powder, comprise the following steps:
A () is according to chemical general formula Sr
xa
ysiO
5: Eu
z, D
min the mol ratio of each element take the fusing assistant that oxide compound containing Sr, A, Si, Eu, D element or carbonate and mole number are described Si mole number 0.01-0.1, mixing, grinding, obtains mixture;
B mixture is warming up to 1350-1500 DEG C by () under reducing atmosphere condition, insulation 3-8h, is incubated preferred 5-7h, is cooled to room temperature, obtain fluorescent material crude product;
C described fluorescent material crude product grinds by (), sieve, pickling, drying, obtain alkaline earth metal silicate Huang-orange fluorescent powder.
In chemical general formula described in step (a) of the present invention, elements Sr and A take corresponding carbonate, and Si, Eu and D take corresponding oxide compound.
Fusing assistant described in step (a) of the present invention is alkaline earth compound CaCl
2, MgCl
2, BaCl
2, CaF
2, MgF
2, BaF
2in the mixture of one or more arbitrary proportions.
Batch mixing milling time described in step (a) of the present invention is 7-15h, preferred 10h.Under preferred processing condition, raw material mixing evenly, and product crystallization is better.
Reducing atmosphere described in step (b) of the present invention refers to H
2atmosphere or N
2, H
2the reducing atmosphere that mixed gas is formed, scope is 75-95:25-5, preferably N
2and H
2volume ratio be 3:1.
Fast cooling speed described in step (b) of the present invention is 30 ~ 40 DEG C/min, preferably 35 DEG C/min.
The described pickling of step (c) of the present invention refers to that it is in the aqueous citric acid solution of 2% that the fluorescent material after sieving is joined mass percent, obtain the phosphor suspension that mass percent is 20%, be heated to 70 DEG C, insulation, stir 60min, then be washed till neutrality with deionized water.
The temperature of the described oven dry of step (c) of the present invention is 50-80 DEG C, and the time is 5-10h, preferably 70 DEG C, 8h.
Described alkaline earth metal silicate Huang-orange fluorescent powder prepared by the present invention can launch the Huang-orange-colored light of 571-612nm at blue-light excited lower Absorbable organic halogens, and light conversion efficiency is high, wider, the luminous relative brightness of peak width at half height is strong, can be used widely in LED illumination or indicating system.
The present invention take silicate as matrix, by the codoped of element-specific and specified proportion, adopts high temperature solid-state method one-step synthesis can effectively absorb the concurrent fluorescent material penetrating Huang-orange-colored light of luminous energy at blue wave band under reducing atmosphere.Detect proof by experiment, alkaline earth metal silicate Huang-orange fluorescent powder prepared by the present invention has wider emmission spectrum and peak width at half height, its centre wavelength can be adjustable between 571 ~ 612nm, granularity is at 8-14 μm, be evenly distributed, narrow distribution range, advantages of good crystallization is a kind of superfine fluorescent powder being applicable to high colour developing illumination and field of backlights use thereof.And the preparation method of alkaline earth metal silicate Huang-orange fluorescent powder provided by the present invention is simple and easy to control, in preparation process, required sintering temperature is lower, and process window is wide, is suitable for large-scale industrial production.
Specifically, the fluorescent material that fluorescent material prepared by the present invention is prepared compared with prior art is compared, and has the following advantages:
(1) fluorescent material prepared by the present invention is by the adjustment of the different doping of matrix element Sr, Ba, Ca, Mg, compared with the fluorescent material disclosed in CN102286282B, widen the emmission spectrum scope of fluorescent material, centre wavelength moves between 571 ~ 612nm, add peak width at half height, can be used for the coating of multiple color temperatures white light LEDs, and make up the deficiency that YAG yellow fluorescent powder in use lacks ruddiness;
(2) the present invention is by the codoped of micro-Sc, Y, La, Lu and Eu, regulates fluorescent powder crystal field, strengthens fluorescent material matrix to the assimilated efficiency of exciting light, effectively promotes the emissive porwer of fluorescent material; Simultaneously when not affecting light efficiency, lower concentration activator Eu
2+doping, effectively improve fluorescent material temperature quenching characteristic;
(3) the present invention makees fusing assistant with the alkaline earth metal compound of F, Cl, reduce calcination temperature, effectively promote the synthesis of fluorescent material crystalline phase, can while guarantee light efficiency decline, fluorescent material particle diameter is obviously declined, advantages of good crystallization, medium particle diameter is distributed in 8-14 μm, simultaneously narrow particle size distribution, the photochromic consistence that effective lifting white light LEDs makes, and secondary breaking treatment process can be exempted, reduce the loss of finished product, improve yield; And special combination fusing assistant improves chemical stability and the moisture resistance of product, after encapsulation, two 85 light efficiency reduced rates of LED are less than 2%.On the other hand in fluorescent material crystalline phase building-up process, univalent anion can play the effect of charge compensation, improves lattice stability.
(4) the present invention is using silicate as the matrix of fluorescent material, stable chemical nature; And material preparation for the requirement of equipment well below similar fluorescent material, therefore, energy consumption and product cost obviously reduce; Synthesis material wide material sources, simultaneously product easily collecting, without waste water and gas discharge, environmental friendliness, is especially applicable to continuous prodution; Gained fluorescent material can obtain the higher palette warm white light of color developing under blue-light excited.
Visible, fluorescent material provided by the invention effectively can be excited by blue light, and widely uses in white LED illumination system, plasma display panel, orange or other color LED system.
Accompanying drawing explanation
Fig. 1 is the SEM figure of fluorescent material prepared by embodiment 5.
Fig. 2 is the SEM figure of fluorescent material prepared by comparative example 1.
Fig. 3 is the SEM figure of fluorescent material prepared by comparative example 2.
Fig. 4 is the utilizing emitted light spectrogram that the fluorescent material of embodiment 30 and 57 and comparative example 1 and 2 preparation excites at 450 nm.
Fig. 5 is quality change figure in time during comparative example and embodiment are tested two 85.
Fig. 6 is brightness flop figure in time during comparative example and embodiment are tested two 85.
Fig. 7 is x chromaticity coordinates variation diagram in time during comparative example and embodiment are tested two 85.
Embodiment
The chemical general formula of alkaline earth metal silicate Huang-orange fluorescent powder in the present invention is described in detail for Sr below with specific embodiment
xa
ysiO
5eu
z, D
m, E
npreparation method.Cited embodiment and embodiment, just in order to silicate Huang-orange fluorescent powder involved in the present invention and preparation method thereof is described, but the present invention is not limited to this embodiment and embodiment.
Embodiment 1 prepares Sr
2.75ba
0.1mg
0.075ca
0.055siO
5: 0.02Eu, 0.04Y silicate fluorescent powder
According to Sr
2.75ba
0.1mg
0.075ca
0.055siO
5: 0.02Eu, 0.04Y stoichiometric ratio takes SrCO
3, BaCO
3, MgO, CaCO
3, SiO
2, Eu
2o
3, Y
2o
3and the fusing assistant MgCl of 0.04mol
2with the CaCl of 0.04mol
2mix, be placed in corundum crucible with ball mill grinding 10h, crucible is placed in tube furnace, in 3:1, be warming up to 1400 DEG C at shielding gas nitrogen and hydrogen volume ratio, be incubated after 5 hours, high temperature takes out and is down to room temperature fast with 35 DEG C/min, take out fluorescent material crude product to grind, cross 100 mesh sieves, the aqueous citric acid solution being 2% through mass percent concentration again washs, obtain the phosphor suspension that mass percent is 20%, be heated to 70 DEG C, insulated and stirred 60min, sediment deionized water is washed till neutrality, finally in the baking oven of 30 DEG C, dry 2h obtains Sr
2.75ba
0.1mg
0.075ca
0.055siO
5: 0.02Eu, 0.04Y fluorescent material.Measure its peak wavelength, relative brightness and D
50, D
10and D
90, peak width at half height and yield.
Embodiment 2,3 and comparative example 3,4 adopt and embodiment 1 same structure formula raw material and fusing assistant, but heat preservation method difference to some extent, other art treatment is with embodiment 1.K=(D
90-D
10)/D
50for weighing grain graininess degree of uniformity, K value is less, represents that grain graininess is more even.After yield=aftertreatment resulting materials quality (fluorescent material crude product)/aftertreatment before quality (fluorescent material finished product).
The technological temperature table of table 1 embodiment and comparative example
As shown in Table 1, temperature accurately controls 1400 DEG C time, and its overall target result is best.When extremes of temperature, crystallization is bad, and product relative brightness can obviously reduce, and when temperature is too high, particle can be grown up, but particle agglomeration is serious, also can have a strong impact on uniform particles degree and yield.
Embodiment 4,5 and comparative example 5,6 be with embodiment 1 same structure formula raw material, fusing assistant and sintering temperature, but soaking time is different, and other art treatment is with embodiment 1.
Table 2 embodiment and comparative example process time table
As shown in Table 2, soaking time accurately controls when 5h, and its overall target result is best.When soaking time is long, product power consumption can increase, and product particle homogeneity and yield can decline.
Embodiment 6,7 and comparative example 7 adopt and embodiment 1 same structure formula raw material, but rate of temperature fall used difference to some extent, other art treatment is with embodiment 1.
Table 3 embodiment and comparative example rate of temperature fall table
As shown in Table 3, rate of temperature fall accurately controls when 30 DEG C/min, and its overall target result is best.When rate of temperature fall is lower than 30 DEG C/min, in product, easily generate more dephasign SrSiO
4and SrO, and brightness can obviously reduce.
Comparative example 8 and embodiment 9-29 adopt and embodiment 1 same structure formula raw material, but the combination of fusing assistant used and addition difference to some extent, other art treatment is with embodiment 1.
Table 4 is the embodiment 9-29 for a change kind of fusing assistant and doping
As shown in Table 4, CaCl is worked as
2amount remain on 0.03mol, particle uniformity is good, and granular size can control near 10 μm, when adding F
-during ion, particle can obviously be grown up, but broken rear yield can reduce.
The proportioning of various element in following examples adjustment major ingredient, to obtain different emissive porwer, the finished product of granule-morphology, is specially: embodiment 30,35-38 have adjusted the content of Eu; Embodiment 39-50 adds and have adjusted general formula Sr
xa
ysiO
5: Eu
z, D
min D
mamount; Embodiment 51-64 have adjusted general formula Sr
xa
ysiO
5: Eu
z, D
min A
yamount content; Its processing condition and flux selection are with embodiment 1.
The embodiment (unit: mol) of table 5 for a change each element ratio
Comparative example 1
With Sr disclosed in patent of invention CN102286282B
1.79lu
0.05ba
0.09siO
4: 0.07Eu
2+repeat experiment as a comparison.
Fluorescent material Sr
1.79lu
0.05ba
0.09siO
4: 0.07Eu
2+concrete preparation method be:
By the 850 DEG C of pre-burnings 2 hours in High Temperature Furnaces Heating Apparatus of europium sesquioxide, lanthanum trioxide, removing moisture wherein and impurity.By general formula Sr
1.79lu
0.05ba
0.09siO
4: 0.07Eu
2+take europium sesquioxide, lutecium oxide, Strontium carbonate powder, barium carbonate, silicon-dioxide respectively, add barium fluoride, barium fluoride addition is 5% of the silicate yellow orange fluorescent powder quality of preparation, with mortar grinder 20 minutes, obtains raw mixture.Being loaded by raw mixture in corundum crucible, be placed in High Temperature Furnaces Heating Apparatus, is in the gas mixture of 1: 50 in the volume ratio of hydrogen and nitrogen, and 1400 DEG C sinter 4 hours, after reaction terminates, naturally cool to room temperature.Added by sintered product in deionized water and be heated to boiling, wash away fusing assistant, repeated washing 3 times, the product after washing puts into baking oven 80 DEG C of dryings 1 hour, by mortar grinder to 500 order fineness, is prepared into silicate yellowish-orange Sr
1.79lu
0.05ba
0.09siO
4: 0.07Eu
2+fluorescent material.
Comparative example 2
With Sr disclosed in patent of invention US7045826
2.93siO
5: 0.07Eu
2+repeat experiment as a comparison.
According to Sr
2.93siO
5: 0.07Eu stoichiometric ratio takes Strontium carbonate powder (SrCO
3), silicon-dioxide (SiO
2) and europium sesquioxide (Eu
2o
3), use acetone to weigh and mixing raw material as solvent, and use ball milling as solvent and Strontium carbonate powder (SrCO
3), silicon-dioxide (SiO
2) and europium sesquioxide (Eu
2o
3) mixing tank of component.Drying temperature is in an oven 120 DEG C, and time of drying is 24 hours, afterwards, described dry mixture to be loaded in rafifinal furnace pot and to heat-treat under the reducing atmosphere of hydrogen mixed gas in electric furnace.In order to form reducing atmosphere, use the gas mixture that hydrogen richness is 5-25%.Thermal treatment temp is 1350 DEG C, and heat treatment time is 40 hours.Finally with mortar grinder to D
50=15.6 μm, be prepared into silicate yellowish-orange Sr
2.93siO
5: 0.07Eu
2+fluorescent material.
The SEM figure of fluorescent material prepared by detection the present invention and fluorescence prepared by comparative example, for embodiment 5 and comparative example 1 and 2, detects the SEM obtained and schemes as shown in Figure 1, Figure 2 and Figure 3; For embodiment 30 and 57 and comparative example 1 and 2, the utilizing emitted light spectrogram that the fluorescent material prepared by detection excites at 450 nm, as shown in Figure 4.
The over-all properties of fluorescent material prepared by detection embodiment of the present invention 35-64 and comparative example, it the results are shown in Table shown in 6.
The inspect on colligated-function result of fluorescent material prepared by table 6 the present invention and comparative example
As can be seen from Table 6, embodiment 30, embodiment 35-38 regulate activator Eu
2+concentration, when concentration is added to 0.05mol, brightness step-down, the easy cancellation of concentration.Its optimum value is 0.02mol.Embodiment 39-embodiment 50 is codopeds of regulating microelement Sc, Y, La, Lu and Eu, by regulating fluorescent powder crystal field, at lower concentration activator Eu
2+doping under, the effective emissive porwer promoting fluorescent material, its optimum doping concentration is the Y of 0.04mol.Embodiment 51-embodiment 64 is the amounts regulating alkaline-earth metal in matrix, and Ba, Mg replace the case of Sr, from result, its brightness is all higher than comparative example, and peak width at half height is greater than the peak width at half height of ratio, simultaneously, part Sr is replaced with a small amount of Ca, make red shift of the emission spectra, widened the emmission spectrum scope of fluorescent material, centre wavelength moves between 571 ~ 612nm.
Result display embodiment 30 best results.Uniform particles, its crude product is when aftertreatment substantially without broken, and product yield is high.
It is 85 DEG C that product obtained in sample in comparative example 1, comparative example 2 and embodiment 30 is taken 10g respectively in temperature, and humidity is carry out two 85 experiments under the environment of 85%, is interrupted and carries out 1000h, to detect its stability.Main Testing index is the change of quality, the change of x chromaticity coordinates, the change of brightness.The change of a monitoring index is detected every 200h.Experimental result is as shown in table 7.
Table 7: in two 85 experiments, comparative example and embodiment quality change in time, brightness flop, x chromaticity coordinates change
As represent respectively in accompanying drawing 5, Fig. 6, Fig. 7 be in two 85 experiments by the sample of comparative example and embodiment with the carrying out of experimental period to the detected result of quality, brightness and the change of x chromaticity coordinates, from figure, the stability of embodiment 30 is than the good stability of comparative example 1 and comparative example 2.
Claims (10)
1. alkaline earth metal silicate Huang-orange fluorescent powder, is characterized in that, the chemical general formula of this fluorescent material is Sr
xa
ysiO
5: Eu
z, D
m; In formula, A is at least one in Ba, Ca and Mg, and D is the one in Sc, Y, La, Lu, and 2.2≤x < 3,0≤y≤0.7,0.005≤z≤0.05,0.005≤m≤0.1, x+y+z=3.
2. a preparation method for alkaline earth metal silicate Huang-orange fluorescent powder, is characterized in that, comprise the following steps:
A () is according to claim 1 chemical general formula Sr
xa
ysiO
5: Eu
z, D
m, in the mol ratio of each element take the fusing assistant that oxide compound containing Sr, A, Si, Eu, D or carbonate and mole number are described Si mole number 0.01-0.1, mixing, grinding, obtains mixture;
B mixture is warming up to 1350-1500 DEG C by () under reducing atmosphere condition, insulation 3-8h, is quickly cooled to room temperature, obtains fluorescent material crude product;
C described fluorescent material crude product grinds by (), sieve, pickling, drying, obtain alkaline earth metal silicate Huang-orange fluorescent powder.
3. the preparation method of alkaline earth metal silicate Huang-orange fluorescent powder according to claim 2, it is characterized in that, in the chemical general formula described in step (a), elements Sr and A take corresponding carbonate or oxide compound, and Si, Eu and D take corresponding oxide compound.
4. the preparation method of alkaline earth metal silicate Huang-orange fluorescent powder according to claim 3, it is characterized in that, the fusing assistant described in step (a) is alkaline earth compound CaCl
2, MgCl
2, BaCl
2, CaF
2, MgF
2, BaF
2in the mixture of one or more arbitrary proportions.
5. the preparation method of alkaline earth metal silicate Huang-orange fluorescent powder according to claim 2, it is characterized in that, the milling time described in step (a) is 7-15h.
6. the preparation method of alkaline earth metal silicate Huang-orange fluorescent powder according to claim 2, it is characterized in that, the reducing atmosphere described in step (b) refers to N
2, H
2the reducing atmosphere that mixed gas is formed.
7. the preparation method of alkaline earth metal silicate Huang-orange fluorescent powder according to claim 2, is characterized in that, the rate of temperature fall of the described quick cooling of step (b) is 30-40 DEG C/min.
8. the preparation method of the alkaline earth metal silicate Huang-orange fluorescent powder according to claim 2,3,4,5,6 or 7, it is characterized in that, the described pickling of step (c) refers to that it is in the aqueous citric acid solution of 2% that the fluorescent material after sieving is joined mass percent, obtain the phosphor suspension that mass percent is 20%, be heated to 70 DEG C, insulated and stirred 60min, then be washed till neutrality with deionized water.
9. the preparation method of the alkaline earth metal silicate Huang-orange fluorescent powder according to claim 2,3,4,5,6 or 7, it is characterized in that, the described drying of step (c) refers to the fluorescent material vacuum-drying after by pickling, temperature 50-80 DEG C, the time is 5-10h.
10. alkaline earth metal silicate Huang-fluorescent orange pruinescence according to claim 1 blue-light excited under illumination or indicating system in application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433639A (en) * | 2016-10-13 | 2017-02-22 | 河北利福光电技术有限公司 | 315 phase orange silicate fluorescent powder and preparation method thereof |
| CN110003893A (en) * | 2019-04-08 | 2019-07-12 | 北京科技大学 | A kind of yellow-orange long after glow luminous material of SiGe hydrochlorate and preparation method |
| CN116768605A (en) * | 2022-03-10 | 2023-09-19 | 中国科学院上海硅酸盐研究所 | Silicate orange complex-phase fluorescent ceramic and preparation method thereof |
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| CN110003893A (en) * | 2019-04-08 | 2019-07-12 | 北京科技大学 | A kind of yellow-orange long after glow luminous material of SiGe hydrochlorate and preparation method |
| CN110003893B (en) * | 2019-04-08 | 2020-09-11 | 北京科技大学 | Silicate of silicon yellow-orange long persistence luminescent material and preparation method |
| CN116768605A (en) * | 2022-03-10 | 2023-09-19 | 中国科学院上海硅酸盐研究所 | Silicate orange complex-phase fluorescent ceramic and preparation method thereof |
| CN116768605B (en) * | 2022-03-10 | 2024-03-12 | 中国科学院上海硅酸盐研究所 | Silicate orange complex-phase fluorescent ceramic and preparation method thereof |
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