CN103773362A - Calcium metasilicate luminous material and preparation method for same - Google Patents
Calcium metasilicate luminous material and preparation method for same Download PDFInfo
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Abstract
The invention discloses a calcium metasilicate luminous material of which chemical general formula is Ca1-x-ySiO3:Pbx,Mny,Mz, wherein M is doped in Ca1-x-ySiO3; M in Pbx,Mny is at least one of Ag, Au, Pt, Pd and Cu metal nanoparticles; x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.1, z is the molar ratio of M and Si, and z is more than 0 and less than or equal to 1*10<-2>. The invention further provides a preparation method for the calcium metasilicate luminous material. According to the calcium metasilicate luminous material and the preparation method thereof, metasilicic acid is used as a luminous substrate, lead is used as a fluorescent sensitizer, manganese is used as a fluorescent activator, and the metal nanoparticles are doped to enhance the luminous efficiency; moreover, the calcium metasilicate luminous material has the advantages of high stability and high luminous intensity.
Description
Technical field
The present invention relates to luminescent material technical field, particularly relate to calcium metasilicate luminescent material and preparation method thereof.
Background technology
The sixties in 20th century, Ken Shoulder has proposed the imagination based on field emission cathode array (Field EmissiveArrays, FEAs) electron beam micro device, utilizes FEAs Design and manufacture flat pannel display and light source device.The principle of work of this novel feds with and traditional cathode tube (Cathode-Ray Tube, CRT) similar, by luminous picture or the lighting use of being embodied as of beam bombardment red, green, blue three-color phosphor, this kind of device all has potential advantage at aspects such as brightness, visual angle, time of response, operating temperature range, energy consumptions.
One of key factor of the feds of excellent is preparation high-performance fluorescent material.The fluorescent material that feds adopts is at present mainly used for sulfide series, oxide compound series and the oxysulfide series phosphor powder of conventional cathode ray tube and projection TV teletron.It is higher that sulfide series and oxysulfide series phosphor powder have luminosity, and there is the characteristic of certain electroconductibility, but easily decompose under the bombardment of large beam deflection, emit elemental sulfur and " poison " negative electrode needle point, and generate other throw outs and cover phosphor surface, reduce the luminous efficiency of fluorescent material.Oxide compound, aluminate fluorescent powder stability are good, but also have the not high enough shortcoming of luminous efficiency.
Calcium metasilicate luminescent material, as CaSiO
3: Pb, Mn is a kind of common cathodoluminescence and photoluminescent phosphor, because it has good chemical stability, thermostability and the advantage such as cheap is commonly used, but its luminous efficiency is lower, also needs further to improve.
Summary of the invention
Based on this, have calcium metasilicate luminescent material that a kind of luminous efficiency is higher and preparation method thereof is provided.
A kind of calcium metasilicate luminescent material, has following chemical general formula: have following chemical general formula: Ca
1-x-ysiO
3: Pb
x, Mn
y, M
z, described M is entrained in Ca
1-x-ysiO
3: Pb
x, Mn
yin, described M is at least one in silver (Ag), gold (Au), platinum (Pt), palladium (Pd) and copper (Cu) metal nanoparticle, 0<x≤0.05,0 < y≤0.1, z be M and Si (silicon) mole ratio, 0<z≤1 × 10
-2.
Therein in an embodiment, 0.01≤x≤0.03.
Therein in an embodiment, 0.02≤y≤0.07.
Therein in an embodiment, 1 × 10
-5≤ z≤5 × 10
-3.
A preparation method for calcium metasilicate luminescent material, comprising:
At least one metal salt solution in Ag, Au, Pt, Pd and Cu is mixed and reacted with auxiliary agent and reductive agent, make the colloidal sol that contains M; Described M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle;
According to M and Si mole ratio z, in the colloidal sol that contains M described in aerosil is dissolved to, at 50 ℃ ~ 75 ℃ temperature, stir 0.5h ~ 3h, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5 ~ 4h, the aerosil of the M that obtains adulterating, 0<z≤1 × 10
-2; And
According to Ca
1-x-ysiO
3: Pb
x, Mn
y, M
zeach element mole ratio, take respectively the compound of calcium (Ca), compound, the compound of Mn and the silicon-dioxide (SiO of described doping M of Pb
2) aerogel, after grinding, being warming up to 500 ℃ ~ 900 ℃ calcining 2h ~ 10h, then at 900 ℃ ~ 1500 ℃ temperature, processing 0.5h ~ 6h in reducing atmosphere, furnace cooling is cooled to room temperature, and obtaining chemical general formula is Ca
1-x-ysiO
3: Pb
x, Mn
y, M
zcalcium metasilicate luminescent material, described M is entrained in Ca
1-x-ysiO
3: Pb
x, Mn
yin, 0<x≤0.05,0<y≤0.1.
In an embodiment, in described metal salt solution, the concentration of metal ion is 5 × 10 therein
-4mol/L ~ 2.5 × 10
-2mol/L.
Therein in an embodiment, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate, and the concentration of the addition of described auxiliary agent in the colloidal sol of the described M of containing is 1 × 10
-4g/mL～5 × 10
-2g/mL.
In an embodiment, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride therein, and in the addition of described reductive agent and described metal salt solution, metal ion mol ratio is 0.5:1 ~ 10:1.
In an embodiment, described reducing atmosphere is nitrogen (N therein
2) and hydrogen (H
2) mixed atmosphere, carbon monoxide (CO) atmosphere and hydrogen atmosphere at least one.
In an embodiment, the compound of described Ca is calcium oxide, nitrocalcite, calcium carbonate, lime acetate or caoxalate therein; The compound of described Pb is plumbous oxide, lead nitrate, lead carbonate, lead acetate or lead oxalate; The compound of described Mn is manganese oxide, manganous nitrate, manganous carbonate, manganous acetate or manganous oxalate.
In above-mentioned calcium metasilicate luminescent material and preparation method thereof, take metasilicic acid as luminous host, lead is sensitized fluorescence agent, manganese is luminescent activator, by metal nano particle-doped enhancing luminous efficiency, this metasilicic acid luminescent material has good stability, the advantage that luminous efficiency is high.
Accompanying drawing explanation
Fig. 1 is the calcium metasilicate luminescent material preparation method's of an embodiment schema;
Fig. 2 is the calcium metasilicate luminescent material prepared of embodiment 3 and the traditional luminescent material cathodoluminescence spectrum comparison diagram under 5kv voltage.
Embodiment
Below in conjunction with embodiment and accompanying drawing, calcium metasilicate luminescent material and preparation method thereof is described in further detail.
The calcium metasilicate luminescent material that one embodiment provides is a kind of fluorescent material, and it is the calcium metasilicate luminescent material of having introduced metal nanoparticle, and this calcium metasilicate luminescent material has following chemical general formula: Ca
1-x-ysiO
3: Pb
x, Mn
y, M
z, M is entrained in Ca
1-x-ysiO
3: Pb
x, Mn
yin, M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, 0<x≤0.05,0<y≤0.1, z be M with Si mole ratio, 0<z≤1 × 10
-2.
In other embodiments, the span of x can be 0.01≤x≤0.03.
In other embodiments, the span of y can be 0.02≤y≤0.07.
In other embodiments, the span of z can be 1 × 10
-5≤ z≤5 × 10
-3.
Above-mentioned calcium metasilicate luminescent material can send red fluorescence, the matrix take calcium metasilicate as luminescent material, and take lead as sensitized fluorescence agent, manganese is luminescent activator, by metal nano particle-doped enhancing luminous efficiency.This metasilicic acid luminescent material has good stability simultaneously, the advantage that luminous intensity is high.
Refer to Fig. 1, the preparation method of the calcium metasilicate luminescent material of an embodiment comprises the following steps:
S101, mixes at least one the metal salt solution in Ag, Au, Pt, Pd and Cu react with auxiliary agent and reductive agent, makes the colloidal sol that contains M; M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle.
In the present embodiment, concentration of salt solution is flexible configuration according to actual needs, and in metal salt solution, the concentration of metal ion can be 5 × 10
-4mol/L ~ 2.5 × 10
-2mol/L.Auxiliary agent can be at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.The addition of auxiliary agent is 1 × 10 in the concentration of the colloidal sol that contains M
-4g/mL～5 × 10
-2g/mL, adds auxiliary agent and can prevent metal nanoparticle reunion.Reductive agent can be at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.The mol ratio of the addition of reductive agent and the metal ion of metal salt solution can be 0.5:1 ~ 10:1.Reaction times can be 10 minutes ~ 45 minutes.
S102, according to M and Si mole ratio z, aerosil is dissolved in the colloidal sol that contains M, at 50 ℃ ~ 75 ℃ temperature, stir 0.5 ~ 3h, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5 ~ 4h, obtain the adulterating aerosil of M, 0<z≤1 × 10
-2.
In the present embodiment, ultrasonic can be under the power of 500W ultrasonic about 10 minutes.Dry can be to be to carry out under 60 ℃ ~ 150 ℃ conditions in temperature.In this process, because aerosil has nanoporous network structure, be well behaved light porous amorphous solid material, its porosity is up to 80% ~ 99.8%, and specific surface area is up to 200m
2/ g ~ 1000m
2/ g, therefore can be combined with metal nanoparticle preferably, forms the aerosil of doping M.
S103, according to Ca
1-x-ysiO
3: Pb
x, Mn
y, M
zeach element mole ratio, take respectively the compound of Ca, compound, the compound of Mn and the aerosil of doping M of Pb, after grinding, be warming up to 500 ℃ ~ 900 ℃ calcining 2h ~ 10h, in reducing atmosphere, at 900 ℃ ~ 1500 ℃ temperature, process 0.5h ~ 6h again, furnace cooling is cooled to room temperature, and obtaining chemical general formula is Ca
1-x-ysiO
3: Pb
x, Mn
y, M
zcalcium metasilicate luminescent material, M is entrained in Ca
1-x-ysiO
3: Pb
x, Mn
yin, 0<x≤0.05,0<y≤0.1.
In the present embodiment, reducing atmosphere can be at least one in the medium weakly reducing atmosphere of mixed atmosphere, carbon monoxide atmosphere and hydrogen atmosphere of nitrogen and hydrogen.In weakly reducing atmosphere, the metal ion of high valence state can be reduced into the metal ion of lower valency, or protection metal ion is not oxidized.The compound of Ca can be calcium oxide, nitrocalcite, calcium carbonate, lime acetate or caoxalate; The compound of Pb can be plumbous oxide, lead nitrate, lead carbonate, lead acetate or lead oxalate; The compound of Mn can be manganese oxide, manganous nitrate, manganous carbonate, manganous acetate or manganous oxalate.
In the preparation method of above-mentioned calcium metasilicate luminescent material, the colloidal sol that first preparation contains metal nanoparticle, then adopt aerosil adsorbing metal nanoparticle, obtain the alumina aerogels doped with metal nanoparticle, prepare again metal nano particle-doped calcium metasilicate luminescent material take the alumina aerogels doped with metal nanoparticle as raw material, by the metal nano particle-doped luminous efficiency that improves luminescent material.Above-mentioned preparation method's technique is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Describe below in conjunction with specific embodiment.
Embodiment 1
Take 41.2mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 16.7mL; After hydrochloro-auric acid dissolves completely, take 400mg Trisodium Citrate and 600mg cetyl trimethylammonium bromide, and be dissolved in aqueous solution of chloraurate under the environment of magnetic agitation; Take 1.9mg sodium borohydride and 17.6mg xitix is dissolved into respectively in 10mL deionized water, obtaining 10mL concentration is 5 × 10
-3the sodium borohydride aqueous solution of mol/L and 10mL concentration are 1 × 10
-2the aqueous ascorbic acid of mol/L; Under the environment of magnetic agitation, first in aqueous solution of chloraurate, add 0.08mL sodium borohydride aqueous solution, stirring reaction adds 3.22mL1 × 10 after 5 minutes again in aqueous solution of chloraurate
-2the aqueous ascorbic acid of mol/L, continues reaction 30 minutes afterwards, and obtaining 20mLAu content is 5 × 10
-3the Au nanoparticle sol of mol/L.
Take aerosil 0.3005g, being dissolved into 10mLAu content is 5 × 10
-3in the Au nanoparticle sol of mol/L, at 50 ℃, stir 3h, then ultrasonic 10 minutes, then be dried at 60 ℃, dried sample is ground evenly, precalcining 4h at 600 ℃, obtains the aerosil that contains Au nanoparticle.
Take 0.2064g calcium oxide (CaO), 0.0089g plumbous oxide (PbO), 0.0243g Manganse Dioxide (MnO
2) and the aerosil that contains Au nanoparticle of 0.2524g, being placed in agate mortar is fully ground to and mixes, then by powder transfer in corundum crucible, 500 ℃ of thermal treatment 10h in retort furnace, again in tube furnace under carbon reducing agent atmosphere 1000 ℃ of thermal reduction 2h, be cooled to room temperature, the luminescent material of the Au nanoparticle that can obtain adulterating
preparation:
Take 25.9mg Platinic chloride (H
2ptCl
66H
2o) be dissolved in the deionized water of 17mL; After Platinic chloride dissolves completely, take 40.0mg Trisodium Citrate and 60.0mg sodium laurylsulfonate, and be dissolved in chloroplatinic acid aqueous solution under the environment of magnetic agitation; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining 10mL concentration is 5 × 10
-3the sodium borohydride aqueous solution of mol/L, prepare 10mL concentration is 5 × 10 simultaneously
-2the hydrazine hydrate solution of mol/L; Under the environment of magnetic agitation, first in chloroplatinic acid aqueous solution, drip 0.4mL sodium borohydride aqueous solution, stirring reaction 5 minutes, and then drip 2.6mL5 × 10 in chloroplatinic acid aqueous solution
-2the hydrazine hydrate solution of mol/L, continues reaction 40 minutes afterwards, and obtaining 20mLPt content is 2.5 × 10
-3the Pt nanoparticle sol of mol/L.
Take aerosil 0.3005g, being dissolved into 10mLPt content is 2.5 × 10
-3in the Pt nanoparticle sol of mol/L, at 75 ℃, stir 0.5h, then ultrasonic 10 minutes, then be dried at 150 ℃, dried sample is ground evenly, precalcining 0.5h at 1200 ℃, obtains the aerosil that contains Pt nanoparticle.
Take 0.3803g calcium carbonate (CaCO
3), 0.0320g lead carbonate (PbCO
3), 0.0092g manganous carbonate (MnCO
3) and the aerosil that contains Pt nanoparticle of 0.2524g, being placed in agate mortar is fully ground to and mixes, then by powder transfer in corundum crucible, 900 ℃ of thermal treatment 2h in retort furnace, again in tube furnace under CO reducing atmosphere 1500 ℃ of thermal reduction 0.5h, be cooled to room temperature, the luminescent material of the Pt nanoparticle that can obtain adulterating
Embodiment 3
Take 3.4mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 42mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 × 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 1.6mL1.5 × 10 that add in silver nitrate aqueous solution
-2the sodium borohydride aqueous solution of mol/L, continues reaction 10 minutes afterwards, and obtaining 20mLAg content is 1 × 10
-3the Ag nanoparticle sol of mol/L.
Take aerosil 0.7212g, being dissolved into 3mLAg content is 1 × 10
-3in the Ag nanoparticle sol of mol/L, at 60 ℃, stir 2h, then ultrasonic 10 minutes, then be dried at 80 ℃, dried sample is ground evenly, precalcining 2h at 800 ℃, obtains the aerosil that contains Ag nanoparticle.
Take 0.5947g lime acetate (Ca (CH
3cOO)
2), 0.0379g lead acetate (Pb (CH
3cOO)
2), 0.0343g manganous acetate Mn ((CH
3cOO)
2) and the aerosil that contains Ag nanoparticle of 0.2524g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, 900 ℃ of thermal treatment 2h in retort furnace, then the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1200 ℃ of thermal reduction 4h of weakly reducing atmosphere, are cooled to room temperature, the luminescent material of the Ag nanoparticle that can obtain adulterating
The luminescent material of the doping Ag nanoparticle of preparing for the present embodiment as shown in Figure 2,
with not metal nano particle-doped luminescent material Ca
0.94siO
3: Pb
0.025, Mn
0.035cathodoluminescence spectrum comparison diagram under 5kv voltage, wherein curve 1 is the luminescent material of doping Ag nanoparticle
luminescent spectrum, curve 2 is not metal nano particle-doped luminescent material Ca
0.94siO
3: Pb
0.025, Mn
0.035luminescent spectrum.As can be seen from the figure at the emission peak at 650nm place, the luminescent material of doping Ag nanoparticle
the luminous intensity of the more not metal nano particle-doped luminescent material of luminous intensity strengthened 39%.
Embodiment 4
Take 0.22mg Palladous chloride (PdCl
22H
2o) be dissolved in the deionized water of 10mL; After Palladous chloride dissolves completely, take 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate, and be dissolved in palladium chloride aqueous solution under the environment of magnetic agitation; Take 0.38mg sodium borohydride molten in 10mL deionized water, obtaining concentration is 1 × 10
-3the sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, in palladium chloride aqueous solution, add fast 10mL1 × 10
-3the sodium borohydride aqueous solution of mol/L, continues reaction 20 minutes afterwards, and obtaining 20mLPd content is 5 × 10
-5the Pd nanoparticle sol of mol/L.
Take aerosil 0.9015g, being dissolved into 3mLPd content is 5 × 10
-5in the Pd nanoparticle sol of mol/L, at 65 ℃, stir 1.5h, then ultrasonic 10 minutes, then be dried at 120 ℃, dried sample is ground evenly, precalcining 2h at 1100 ℃, obtains the aerosil that contains Pd nanoparticle.
Take 0.4745g caoxalate (CaC
2o
4), 0.0094g lead oxalate (PbC
2o
4), 0.0377g manganous oxalate (MnC
2o
4) and the aerosil that contains Pd nanoparticle of 0.2524g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, 700 ℃ of thermal treatment 5h in retort furnace, then the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1000 ℃ of thermal reduction 6h of weakly reducing atmosphere, are cooled to room temperature, can obtain the luminescent material of doping Pd nanoparticle
Embodiment 5
Take 1.6mg cupric nitrate (Cu (NO
3)
2) be dissolved in the ethanol of 16mL, after dissolving completely, stir while add 2mgPVP, then slowly splash into 0.4mg sodium borohydride molten to obtain in 10mL ethanol 1 × 10
-3the sodium borohydride alcoholic solution 4mL of mol/L, continues stirring reaction 10 minutes, and obtaining 20mLCu content is 4 × 10
-4the nanometer particle colloid of mol/L.
Take aerosil 0.7212g, being dissolved into 3mLCu content is 4 × 10
-4in the nanometer particle colloid of mol/L, at 65 ℃, stir 1.5h, then ultrasonic 10 minutes, then be dried at 110 ℃, dried sample is ground evenly, precalcining 3h at 900 ℃, obtains the aerosil that contains Cu nanoparticle.
Take 0.5612g nitrocalcite (Ca (NO
3)
2), 0.0596g lead nitrate (Pb (NO
3)
2), 0.0980g manganous acetate (Mn (CH
3cOO)
2) and the aerosil that contains Cu nanoparticle of 0.2524g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, 800 ℃ of thermal treatment 8h in retort furnace, then the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1100 ℃ of thermal reduction 5h of weakly reducing atmosphere, are cooled to room temperature, can obtain the luminescent material of doped with Cu nanoparticle
Embodiment 6
Take respectively 0.0429gAgNO
3, 0.0733g Trisodium Citrate, 0.05g polyvinylpyrrolidone, be mixed with respectively the AgNO of 10mL0.025mol/L
3the polyvinylpyrrolidone aqueous solution of the sodium citrate aqueous solution of the aqueous solution, 10mL0.025mol/L and 10mL5mg/mL.Get 2mLAgNO
3the aqueous solution joins in 30mL deionized water, adds above-mentioned polyvinylpyrrolidone aqueous solution 4mL to stir simultaneously, is heated to 100 ℃ and then dropwise adds 4mL sodium citrate aqueous solution, reacts after 15 minutes, and obtaining 40mLAg content is 1.25 × 10
-3the Ag nanoparticle sol of mol/L.
Take aerosil 0.6010g, being dissolved into 4mLAg content is 1.25 × 10
-3in the Ag nanoparticle sol of mol/L, at 70 ℃, stir 1h, then ultrasonic 10 minutes, then 80 ℃ dry, dried sample is ground evenly, precalcining 3h at 800 ℃, obtains the aerosil of Ag nanoparticle.
Take 0.4070g calcium chloride (CaCl
2), 0.0556g lead chloride (PbCl
2), 0.0166g Manganous chloride tetrahydrate (MnCl
2) and the aerosil of the Ag nanoparticle of 0.2524g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, 600 ℃ of thermal treatment 4h in retort furnace, then in tube furnace at pure H
2the lower 1100 ℃ of thermal reduction 3h of reducing atmosphere, are cooled to room temperature, the luminescent material of the Ag nanoparticle that can obtain adulterating
Embodiment 7
Take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2and 2.5mgAgNO O)
3be dissolved in the deionized water of 28mL; After dissolving completely, take 22mg Trisodium Citrate and 20mgPVP, and under the environment of magnetic agitation, be dissolved in above-mentioned mixing solutions; Take freshly prepd 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 × 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 2mL1.5 × 10 that add in above-mentioned mixing solutions
-2the sodium borohydride aqueous solution of mol/L, continues reaction 20 minutes afterwards, and obtaining the total metal concentration of 30mL is 1 × 10
-3the Ag of mol/L
0.5/ Au
0.5nanoparticle sol.
Take aerosil 0.4808g, be dissolved into the total metal concentration 1 × 10 of 10mL
-3mol/LAg
0.5/ Au
0.5in nanoparticle sol, at 75 ℃, stir 1h, then ultrasonic 10 minutes, then be dried at 100 ℃, dried sample is ground evenly, precalcining 4h at 1000 ℃, obtains the aerosil that contains Ag and Au nanoparticle.
Take calcium oxide (CaO) 0.2039g, 0.0223g plumbous oxide (PbO), 0.0229g Manganse Dioxide (MnO
2) and the aerosil that contains Ag and Au nanoparticle of 0.2524g, being placed in agate mortar is fully ground to and mixes, then by powder transfer in corundum crucible, 700 ℃ of thermal treatment 6h in retort furnace, then the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 900 ℃ of thermal reduction 5h of weakly reducing atmosphere, are cooled to room temperature, the luminescent material of can obtain adulterating Ag and Au Nanoalloy
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a calcium metasilicate luminescent material, is characterized in that, has following chemical general formula: Ca
1-x-ysiO
3: Pb
x, Mn
y, M
z, described M is entrained in Ca
1-x-ysiO
3: Pb
x, Mn
yin, described M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, 0<x≤0.05,0<y≤0.1, z be M with Si mole ratio, 0<z≤1 × 10
-2.
2. calcium metasilicate luminescent material according to claim 1, is characterized in that 0.01≤x≤0.03.
3. calcium metasilicate luminescent material according to claim 1, is characterized in that 0.02≤y≤0.07.
4. calcium metasilicate luminescent material according to claim 1, is characterized in that 1 × 10
-5≤ z≤5 × 10
-3.
5. a preparation method for calcium metasilicate luminescent material, is characterized in that, comprising:
At least one metal salt solution in Ag, Au, Pt, Pd and Cu is mixed and reacted with auxiliary agent and reductive agent, make the colloidal sol that contains M; Described M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle;
According to M and Si mole ratio z, in the colloidal sol that contains M described in aerosil is dissolved to, at 50 ℃ ~ 75 ℃ temperature, stir 0.5h ~ 3h, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5 ~ 4h, the aerosil of the M that obtains adulterating, 0<z≤1 × 10
-2; And
According to Ca
1-x-ysiO
3: Pb
x, Mn
y, M
zeach element mole ratio, take respectively the compound of Ca, compound, the compound of Mn and the aerosil of described doping M of Pb, after grinding, be warming up to 500 ℃ ~ 900 ℃ calcining 2h ~ 10h, in reducing atmosphere, at 900 ℃ ~ 1500 ℃ temperature, process 0.5h ~ 6h again, furnace cooling is cooled to room temperature, and obtaining chemical general formula is Ca
1-x-ysiO
3: Pb
x, Mn
y, M
zcalcium metasilicate luminescent material, described M is entrained in Ca
1-x-ysiO
3: Pb
x, Mn
yin, 0<x≤0.05,0<y≤0.1.
6. the preparation method of calcium metasilicate luminescent material according to claim 5, is characterized in that, in described metal salt solution, the concentration of metal ion is 5 × 10
-4mol/L ~ 2.5 × 10
-2mol/L.
7. the preparation method of calcium metasilicate luminescent material according to claim 5, it is characterized in that, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate, and the concentration of the addition of described auxiliary agent in the colloidal sol of the described M of containing is 1 × 10
-4g/mL～5 × 10
-2g/mL.
8. the preparation method of calcium metasilicate luminescent material according to claim 5, it is characterized in that, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride, and the mol ratio of the addition of described reductive agent and the metal ion of described metal salt solution is 0.5:1 ~ 10:1.
9. the preparation method of calcium metasilicate luminescent material according to claim 5, is characterized in that, described reducing atmosphere is at least one in mixed atmosphere, carbon monoxide atmosphere and the hydrogen atmosphere of nitrogen and hydrogen.
10. the preparation method of calcium metasilicate luminescent material according to claim 5, is characterized in that, the compound of described Ca is calcium oxide, nitrocalcite, calcium carbonate, lime acetate or caoxalate; The compound of described Pb is plumbous oxide, lead nitrate, lead carbonate, lead acetate or lead oxalate; The compound of described Mn is manganese oxide, manganous nitrate, manganous carbonate, manganous acetate or manganous oxalate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849378A (en) * | 2012-11-29 | 2014-06-11 | 海洋王照明科技股份有限公司 | Calcium metasilicate red luminescent material and preparation method thereof |
| CN105112045A (en) * | 2015-08-20 | 2015-12-02 | 桂林市环境监测中心站 | Luminescent material containing dielectric layer and metal nanoparticles and preparation method therefor |
| CN109702221A (en) * | 2019-02-01 | 2019-05-03 | 北京弘微纳金科技有限公司 | A kind of preparation method of aerosil load carbon/carbon-copper composite material |
-
2012
- 2012-10-25 CN CN201210413255.1A patent/CN103773362A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849378A (en) * | 2012-11-29 | 2014-06-11 | 海洋王照明科技股份有限公司 | Calcium metasilicate red luminescent material and preparation method thereof |
| CN105112045A (en) * | 2015-08-20 | 2015-12-02 | 桂林市环境监测中心站 | Luminescent material containing dielectric layer and metal nanoparticles and preparation method therefor |
| CN109702221A (en) * | 2019-02-01 | 2019-05-03 | 北京弘微纳金科技有限公司 | A kind of preparation method of aerosil load carbon/carbon-copper composite material |
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