CN100572496C - High brightness red alkaline earth titanate fluorescent powder and reducing atmosphere treatment preparation method thereof thereof - Google Patents
High brightness red alkaline earth titanate fluorescent powder and reducing atmosphere treatment preparation method thereof thereof Download PDFInfo
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- CN100572496C CN100572496C CNB2006100530785A CN200610053078A CN100572496C CN 100572496 C CN100572496 C CN 100572496C CN B2006100530785 A CNB2006100530785 A CN B2006100530785A CN 200610053078 A CN200610053078 A CN 200610053078A CN 100572496 C CN100572496 C CN 100572496C
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Abstract
The invention discloses a kind of high brightness red alkaline earth titanate fluorescent powder and preparation method thereof, regulate and control alkaline earth titanate fluorescent powder matrix defective, thereby improve the luminosity of its burst of ultraviolel and electron-beam excitation by the different atmosphere condition.Its major technique feature is, the high temperature solid state reaction that compound through solid phase mixing material or the preparation of wet-chemical approach is carried out under the reducing atmosphere condition burns till, perhaps burn till the back and introduce the reducing atmosphere aftertreatment technology at air, rare-earth ion activated alkaline earth titanate fluorescent powder matrix defect state is regulated and control, make fluorescent material when burst of ultraviolel and denoted low voltage electron beam excite, have high luminosity and good material use properties, the light-emitting phosphor brightness that the present invention makes improves about order of magnitude, has the stability of material height simultaneously, have no side effect, operating procedure is simple, the characteristics that cost is low can be widely used in field of information display such as electron-beam excitation display screen.
Description
Technical field
The present invention relates to rare-earth ion activated red alkaline earth titanate fluorescent powder of a kind of high brightness and preparation method thereof, refer in particular to rare-earth ion activated red alkaline earth titanate fluorescent powder of high brightness of in firing process or aftertreatment technology, introducing the acquisition of reducing atmosphere processing means and preparation method thereof, belong to materials science field.
Background technology
Along with developing rapidly of modern science and technology, luminescent material develops into by multiple excitaton source stimulated luminescences such as electricity, sound, heat, chemistry, biology, mechanical energy and energetic rays from general photoluminescence, demonstration and an illuminating material, and be widely used in ultra-thin television, liquid crystal and plasma display, the crucial display material of high-tech products such as mini monitor and sophisticated sensor and probe.
In the recent period, Field Emission Display (FED) has obtained flourish as a kind of emerging flat panel display, and is expected to replace conventional cathode ray tube (CRT) technique of display, and FED requires to work under low voltage and high current densities with fluorescent material, traditional C RT fluorescent material is as red Y commonly used
2O
3: Eu fluorescent material is not suitable for FED and shows occasion.At present, (10V～100V) red fluorescence powder of electron-beam excitation mainly is Zn to be used for low pressure
1-xCd
xS (0≤x≤1) system fluorescent material, this fluorescent material has been widely used in vacuum fluorescent display device occasions such as (VFD).Yet, sulfide Zn
1-xCd
xIn use there are some tangible problems in S fluorescent material, decomposes easily as long-time electron beam irradiation postcure matter fluorescent powder, and decomposes S or the SO that produces
2Reduced electron emissivity as the electron source oxide cathode; In addition, a large amount of ruddiness colourity conditioning agent component Cd ion pair human body harmfuls that adopt in this sulphide fluorescent material, European Union considers from the environmental protection equal angles, stipulates to begin to forbid such Zn in July, 2006
1-xCd
xThe S red fluorescence powder, this has caused traditional Z n
1-xCd
xThe Application Areas of S red fluorescence powder is subjected to very big restriction, presses for the searching and the nontoxicity of development of new, the environment-friendly red FED fluorescent material of efficient stable at present.
People such as Vecht in 1994 find the CaTiO of perovskite structure
3: Pr
3+Be a kind of novel red fluorescent material with potential demonstration purposes.1996, people such as Toki found Al (OH)
3Or Ga
2O
3The component codoped can make SrTiO
3: pr
3+About two orders of magnitude of photoluminescence and cathodoluminescence intensity enhancing can be used as the red fluorescence powder material of Field Emission Display (FED) and the luminous demonstration of vacuum electronic (VFD) etc.Therefore, the research and development of titanate substrate fluorescent powder has caused the concern of industrial community.With Zn
1-xCd
xThe S sulphide fluorescent material is compared, and the materials chemistry character of titanate substrate fluorescent powder is highly stable, and when adopting rare earth ion as the luminescence center ion, the glow peak of fluorescent material is single, and purity of color is better, as CaTiO
3: pr
3+Photoluminescence and the chromaticity coordinates of negative ray ruddiness be x=0.680, y=0.311, very approaching with the desirable redness of U.S. NTSC system regulation.Consider that from stability of material and glow color such rare-earth ion activated titanate fluorescent powder is expected to substitute Zn
1-xCd
xThe sulfide red fluorescent material of S becomes the nontoxicity of a new generation, the environment-friendly red FED phosphor material powder of high stable.
But still there is luminosity fundamental issue on the low side in this class material, has limited its application.So far, the patent application of relevant this class fluorescent material is seldom recorded in 2004 and 2005 as big island English and have been applied for patent 2004-097738 and 200510069719.1 in Japan and China respectively.In addition, at CaTiO
3The relation research of the material structure of fluorescent material and luminescent properties, more non-patent literature report is arranged, as non-patent literature 1 (Vecht etc., " New electron excited light emitting materials ", J.Vac.Sci.Tehcnol.B, 12 (2) (1994) p.781), non-patent literature 2 (Diallo etc., " Improvement of theoptical performances of Pr
3+In CaTiO
3", J.Alloys.Comp., 323-324 (2001) are p.218); Or non-patent literature 3 (Kang etc., " The influence of Li addition on Cathodoluminescence ofCaTiO
3: Pr
3+", Eurodisplay (2002) is p.777).
Summarizing present existing patent documentation and non-patent literature report finds, the pyroreaction firing process under traditional air atmosphere is all adopted in all literature research work, and research work relates generally to the luminosity that improves red titanate fluorescent material by doping different sorts monovalence, divalence or trivalent assisting ion, and analyzes and study at material structure and luminescent properties.Although part document and patent report under photoluminescence and the electron-beam excitation light-emitting phosphor brightness be significantly improved, but back phosphor material powder sclerosis, shortcomings such as material expected service life reduction take place to change mutually, burn till in the matrix that easily causes a large amount of dopant ions that for this reason mix.
On the whole, the luminosity of this class material is still lower at present, needs to continue to improve and improve; At this class alkaline earth titanate luminous host, still do not utilize some special preparation process conditions to come the control texture defective at present, thereby obtain the research report of the fluorescent material of high brightness, there is not relevant patent application yet.
Summary of the invention
The present invention seeks to carry out outside the material prescription improvement technological line at the different valence state ion doping that passes through of present broad research, for improving the material service performances such as luminosity of phosphor material powder, proposition utilizes reducing atmosphere to burn till or the reducing atmosphere aftertreatment technology prepares high brightness red alkaline earth titanate fluorescent powder and preparation method thereof.
High brightness red alkaline earth titanate fluorescent powder provided by the invention and preparation method thereof by different atmosphere condition regulation and control red alkaline earth titanate fluorescent powder matrix defective, thereby improves its burst of ultraviolel and electron-beam excitation luminosity.Its major technique innovative characteristics is, compound through solid phase batch mixing or the preparation of wet-chemical approach is carried out reducing atmosphere high temperature solid state reaction firing process, or the reducing atmosphere aftertreatment technology after burning till by air atmosphere, rare-earth ion activated alkaline earth titanate fluorescent powder matrix defect state is regulated and control, obtain that denoted low voltage electron beam excites and during burst of ultraviolel fluorescent material have high luminosity and good material use properties.
The invention provides a kind of high brightness red alkaline earth titanate fluorescent powder by reducing atmosphere controlled material defective, its prescription composition formula is: ATiO
3: xRe, yM; Wherein A is a kind of of alkaline earths Ca, Sr, Ba element, promptly with CaTiO
3, SrTiO
3Or BaTiO
3Alkaline earth titanate is a luminous host; Re is Doped Rare Earth luminescence center ion (or claiming rare-earth ion activated dose), is among cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; 0＜x＜0.15,0≤y＜0.4, M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In or lithium Li, sodium Na, the potassium K one or more.
A kind of preparation method of high brightness red alkaline earth titanate fluorescent powder may further comprise the steps:
1) burns till with the preparation of solid phase batch mixing method or wet-chemical reaction method and use compound;
2) adopt high temperature reduction atmosphere firing process or reducing atmosphere aftertreatment technology to burn till processing, obtain to burn till the fluorescence powder burning till with compound;
3) be 1: 0.5～2.5 adding dehydrated alcohols by the weight ratio of burning till fluorescence powder and dehydrated alcohol, at rotating speed is that ball milling mixes 4～24h in 50～250r/min planetary ball mill, the ball milling material was dried 6～24 hours in 50～150 ℃ of baking ovens, after oven dry material sieves promptly.
Described solid reaction process is: the compound with alkaline earth carbonate, titanium dioxide, rare earth nitrate, supplementary doping element M is a raw material, is ATiO by atomic ratio
3: xRe, yM take by weighing each raw material, and wherein A is Ca, Sr or Ba, and Re is a Doped Rare Earth luminescence center ion, are among cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more; Weight ratio by raw material and deionized water is 1: 0.5～1.5, adds deionized water, and ball milling mixes 2～36h in rotating speed 200r/min planetary ball mill, and the ball milling material was dried 6～36 hours in 50～150 ℃ of baking ovens, promptly got to burn till to use compound.
Described wet-chemical reaction method is: adopting the compound of alkaline earth nitrate, butyl (tetra) titanate, rare earth nitrate and supplementary doping element M is raw material, and is assistant chemical reagent with hexanaphthene, polyoxyethylene glycol Octyl Ether and methyl ethyl diketone; By atomic ratio is ATiO
3: xRe, yM take by weighing each raw material, and wherein A is Ca, Sr or Ba, and Re is a Doped Rare Earth luminescence center ion, are among cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more; The rare earth nitrate raw material is added appropriate amount of deionized water, and being mixed with rare earth ion concentration is that 0.5～2.0mol/L, pH are 2～6 rare earth nitrate solution; Get and add 50～150ml hexanaphthene, agitation condition adds 10～50ml surfactant polyethylene Octyl Ether down, add the nitric acid diluent of pressing atom proportioning blended rare earth nitrate solution 2～10ml, alkaline earth nitrate solution and supplementary doping element compound then, add again primary isoamyl alcohol to solution transparent till, continue to stir 10～60 minutes; The butyl (tetra) titanate raw material that adds again by the proportioning weighing is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel main body of homogeneous transparent at last, it 50-250 ℃ of drying, is promptly got to burn till after the exsiccant xerogel grinds and use compound.
Described alkaline earth carbonate is CaCO
3, SrCO
3Or BaCO
3In one or more.
Described alkaline earth nitrate is Ca (NO
3)
2, Sr (NO
3)
2Or Ba (NO
3)
2In one or more.
Described rare earth nitrate is Pr (NO
3)
3, Ce (NO
3)
3, Eu (NO
3)
3, Tb (NO
3)
3, Er (NO
3)
3Or Tm (NO
3)
3One or both.
The compound of described supplementary doping element M is oxide compound, oxyhydroxide or the carbonate cpds of supplementary doping element M.
Described high temperature reduction atmosphere firing process is: will burn till plumbago crucible or the corundum matter tube furnace of directly putting into favorable sealing property with compound, logical CO, N
2, H
2Or NH
3In a kind of gas or its mixed gas, as nitrogen/hydrogen gas mixture reducing gas, begin to be warming up to 800～1400 ℃ from room temperature with 10 ℃/min, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, after insulation finishes, keep the reducing atmosphere furnace cooling to obtain to burn till the fluorescence powder to room temperature.
Described reducing atmosphere aftertreatment technology is: will burn till with compound and put into high-temperature electric resistance furnace, begin to be warming up to 1000～1400 ℃ from room temperature with 10 ℃/min, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, insulation finishes the back furnace cooling and obtains fluorescent material; Then fluorescent material is put into the plumbago crucible or the corundum matter tube furnace of favorable sealing property, logical CO, N
2, H
2Or NH
3In a kind of gas or its mixed gas, as nitrogen/hydrogen gas mixture reducing gas, begin to be warming up to 600～1100 ℃ from room temperature with 10 ℃/min, carried out sufficient reducing atmosphere aftertreatment reaction in 2～10 hours in the post-processing temperature insulation of setting, insulation finishes the back and keeps the reducing atmosphere furnace cooling to obtain to burn till the fluorescence powder to room temperature.
The present invention can introduce reducing atmosphere processing means regulation and control red alkaline earth titanate fluorescent powder matrix structure defective in burning till treatment process, improve the luminous intensity of the luminous and burst of ultraviolel of the electron-beam excitation of fluorescent material.The red alkaline earth titanate fluorescent powder of the present invention's preparation has good material behaviors such as red luminous performance, is a kind of red fluorescence powder material that has development prospect.Compare with the preparation method and the material property of research both at home and abroad at present and use electron-beam excitation red fluorescence powder, the present invention has following characteristics:
1) with traditional Z n
1-xCd
xS fluorescent material is compared, and has the stability of material height, has no side effect, and the advantage of non-environmental-pollution is with a wide range of applications.
2) compare with the red alkaline earth titanate fluorescent powder that normal atmospheric atmosphere is burnt till, the luminous intensity that high temperature reduction technology or reducing atmosphere aftertreatment technology burn till fluorescent material improves an order of magnitude, can overcome phosphorescent substance matrix that mix a large amount of assisting ions and higher firing temperature bring and easily produce phase transformation, the material not problem of easy grinding of hardening.
3) material technology is stable, and can effectively control some trap kind and number in the luminous host by regulation and control atmosphere kind, the gentle flow condition of proportioning, and material luminous intensity and persistence characteristic are regulated and optimized.
4), can develop and a kind of fluorescent material new preparation process that dopant ion just effectively improves such phosphor luminescence performance that need not based on this type of reduction firing process.
Embodiment
Below in conjunction with embodiment the present invention is further described.Wherein embodiment 1-12 is the reducing atmosphere firing process, and embodiment 13-24 is for adopting the reducing atmosphere aftertreatment technology.
Embodiment 1
With chemical pure or analytical pure lime carbonate CaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ca: Ti: Pr takes by weighing each preparation of raw material compound at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, control rotating speed 200r/min ball milling 4h in planetary ball mill, the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk places in the plumbago crucible, be warming up to 1200 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets the CaTiO that burns till in the CO reducing atmosphere after the oven dry material sieves
3: the 0.002Pr phosphor material powder.
Embodiment 2
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk places in the plumbago crucible, be warming up to 1200 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets the SrTiO that burns till in the CO reducing atmosphere after the oven dry material sieves
3: the 0.002Pr fluorescent material.
Embodiment 3
With chemical pure or analytical pure barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ba: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/mi ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk places in the plumbago crucible, be warming up to 1200 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets the BaTiO that burns till in the CO reducing atmosphere after the oven dry material sieves
3: the 0.002Pr fluorescent material.
Embodiment 4
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.Oven dry material takes by weighing by every part of 5g, depresses to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, and disk places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds N
2: H
2=9: 1 mixed atmosphere, overall flow rate is 100ml/min, be warming up to 1200 ℃ with 10 ℃/min, being incubated 2～3 hours burns till, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got in N after the oven dry material sieves
2/ H
2Mix the SrTiO that reducing atmosphere burns till
3: the 0.002Pr fluorescent material.
Embodiment 5
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.Oven dry material takes by weighing by every part of 5g, depresses to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds N
2: H
2=1: 9 mixed atmosphere, overall flow rate is 100ml/min, be warming up to 1200 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got in N after the oven dry material sieves
2/ H
2Mix the SrTiO that reducing atmosphere burns till
3: the 0.002Pr fluorescent material.
Embodiment 6
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.Oven dry material takes by weighing by every part of 5g, depresses to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds N
2: H
2=9: 1 mixed atmosphere, overall flow rate is 300ml/min, be warming up to 1200 ℃ with 10 ℃/min, being incubated 3 hours burns till, making and burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got N after the oven dry material sieves
2/ H
2Mix the SrTiO that reducing atmosphere burns till
3: the 0.002Pr fluorescent material.
Embodiment 7
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.Oven dry material takes by weighing by every part of 5g, depresses to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds pure N
2Atmosphere, overall flow rate is 100ml/min, be warming up to 1200 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got at pure N after the oven dry material sieves
2The SrTiO that reducing atmosphere burns till
3: the 0.002Pr fluorescent material.
Embodiment 8
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.Oven dry material takes by weighing by every part of 5g, depresses to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds pure H
2Atmosphere, overall flow rate is 100ml/min, be warming up to 1200 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got at pure H after the oven dry material sieves
2The SrTiO that reducing atmosphere burns till
3: the 0.002Pr fluorescent material.
Embodiment 9
With chemical pure or analytical pure lime carbonate CaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ca: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.Oven dry material takes by weighing by every part of 5g, depresses to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds pure H
2Atmosphere, overall flow rate is 100ml/min, be warming up to 1200 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got at pure H after the oven dry material sieves
2The CaTiO that reducing atmosphere burns till
3: the 0.002Pr fluorescent material.
Embodiment 10
With chemical pure or analytical pure lime carbonate CaCO
3, titanium dioxide TiO
2, hydroxide Al (OH
3)
3With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ca: Ti: Pr: Al is 1: 1: 0.002: 0.25 takes by weighing each preparation of raw material admixtion, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, place in the plumbago crucible, be warming up to 1200 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets the CaTiO that burns till at the CO reducing atmosphere after the oven dry material sieves
3: 0.002Pr, 0.25Al fluorescent material.
Embodiment 11
With chemical pure or analytical pure hexanaphthene, polyoxyethylene glycol Octyl Ether, praseodymium nitrate Pr (NO
3)
3, strontium nitrate Sr (NO
3)
2, butyl (tetra) titanate, aluminum nitrate Al (NO
3)
3With methyl ethyl diketone be raw material, be 1: 1: 0.002 by Sr: Ti: Pr: Al: 0.25 takes by weighing each preparation of raw material admixtion.Earlier with praseodymium nitrate Pr (NO
3)
3Be dissolved in the 100ml beaker, add appropriate amount of deionized water and be heated to dissolving fully, adjusting PH is 3～4, and solution Pr ionic concn is decided to be 1.0mol/L.Add the 100ml hexanaphthene, agitation condition adds 20ml surfactant polyethylene Octyl Ether down, adds then by proportioning and mixes 10ml Pr (NO
3)
3Solution and an amount of Sr (NO
3)
2With Al (NO
3)
3Solution, add again a spot of primary isoamyl alcohol to solution transparent till, continue to stir 30 minutes.Adding butyl (tetra) titanate is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel of homogeneous transparent at last, gel is placed 80 ℃ of dryings, dried xerogel takes out to grind and obtains burning till the wet-mixed material of usefulness, compound places in the alumina crucible, puts into the corundum ceramic pipe of sealing, feeds pure H
2Gas, flow velocity is 100ml/min, burnt till 3 hours in 1100 ℃, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets at pure H after the oven dry material sieves
2The SrTiO that burns till under the reducing atmosphere
3: 0.002Pr, 0.25Al phosphor material powder.
Embodiment 12
With chemical pure or analytical pure hexanaphthene, polyoxyethylene glycol Octyl Ether, praseodymium nitrate Pr (NO
3)
3, strontium nitrate Sr (NO
3)
2, butyl (tetra) titanate, aluminum nitrate Al (NO
3)
3With methyl ethyl diketone be raw material, be 1: 1: 0.002 by Sr: Ti: Pr: Al: 0.25 takes by weighing each preparation of raw material admixtion.Earlier with praseodymium nitrate Pr (NO
3)
3Be dissolved in the 50ml beaker, add appropriate amount of deionized water and be heated to dissolving fully, adjusting pH is 3～4, and solution Pr ionic concn is decided to be 1.0mol/L.Add the 100ml hexanaphthene, agitation condition adds 20ml surfactant polyethylene Octyl Ether down, adds then by proportioning and mixes 10ml Pr (NO
3)
3Solution and an amount of Sr (NO
3)
2With Al (NO
3)
3Solution, add again a spot of primary isoamyl alcohol to solution transparent till, continue to stir 30 minutes.Adding butyl (tetra) titanate is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel of homogeneous transparent at last, gel is placed 80 ℃ of dryings, dried xerogel takes out to grind and obtains burning till the wet-mixed material of usefulness, compound places in the plumbago crucible, be warming up to 1100 ℃ with 10 ℃/min, be incubated 3 hours, the fluorescence powder that burns till that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets the SrTiO that burns till in the CO reducing atmosphere after the oven dry material sieves
3: 0.002Pr, 0.25Al phosphor material powder.
Embodiment 13
With chemical pure or analytical pure lime carbonate CaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ca: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, control rotating speed 200r/min ball milling 4h in planetary ball mill, the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is put in the corundum crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, putting into the carbon box of sealing handled 6 hours in 800 ℃ of insulations, the fluorescence powder that obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got the CaTiO of CO reducing atmosphere anneal after the oven dry material sieves
3: the 0.002Pr phosphor material powder.
Embodiment 14
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is put in the corundum crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, putting into the carbon box of sealing handled 6 hours in 850 ℃ of insulations, the fluorescence powder that obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got the SrTiO of CO reducing atmosphere anneal after the oven dry material sieves
3: the 0.002Pr phosphor material powder.
Embodiment 15
With chemical pure or analytical pure barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ba: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/mi ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is put in the corundum crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, in air, be incubated 2～3 hours, obtain fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, putting into the carbon box of sealing handled 6 hours in 900 ℃ of insulations, the fluorescence powder that obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got the BaTiO of CO reducing atmosphere anneal after the oven dry material sieves
3: the 0.002Pr phosphor material powder.
Embodiment 16
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is placed in the corundum crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then, place in the alumina crucible, put into the corundum ceramic pipe of sealing, feed N the fluorescent material grind into powder
2: H
2=9: 1 mixed atmosphere, overall flow rate is 100ml/min, being warming up to 850 ℃ of insulations with 10 ℃/min handled 6 hours, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got N after the oven dry material sieves
2/ H
2The SrTiO that mixes the reducing atmosphere aftertreatment
3: the 0.002Pr fluorescent material.
Embodiment 17
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is placed in the alumina crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then, place in the alumina crucible, put into the corundum ceramic pipe of sealing, feed N the fluorescent material grind into powder
2: H
2=1: 9 mixed atmosphere, overall flow rate is 100ml/min, being warming up to 850 ℃ of insulations with 10 ℃/min handled 6 hours, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got N after the oven dry material sieves
2/ H
2The SrTiO that mixes the reducing atmosphere aftertreatment
3: the 0.002Pr fluorescent material.
Embodiment 18
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mr * 3mm in the 150MPa uniaxial compression, disk is placed in the alumina crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then, place in the alumina crucible, put into the corundum ceramic pipe of sealing, feed N the fluorescent material grind into powder
2: H
2=9: 1 mixed atmosphere, overall flow rate is 300ml/min, being warming up to 850 ℃ of insulations with 10 ℃/min handled 6 hours, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got N after the oven dry material sieves
2/ H
2The SrTiO that mixes the reducing atmosphere aftertreatment
3: the 0.002Pr fluorescent material.
Embodiment 19
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is placed in the alumina crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, place in the alumina crucible, put into the corundum ceramic pipe of sealing, feeding overall flow rate is the pure N of 100ml/min
2Gas, being warming up to 850 ℃ of insulations with 10 ℃/min handled 6 hours, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got pure N after the oven dry material sieves
2The SrTiO of atmosphere aftertreatment
3: the 0.002Pr fluorescent material.
Embodiment 20
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Sr: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is placed in the alumina crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, place in the alumina crucible, put into the corundum ceramic pipe of sealing, feeding overall flow rate is the pure H of 100ml/min
2Gas, being warming up to 850 ℃ of insulations with 10 ℃/min handled 6 hours, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got pure H after the oven dry material sieves
2The SrTiO of atmosphere aftertreatment
3: the 0.002Pr fluorescent material.
Embodiment 21
With chemical pure or analytical pure lime carbonate CaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ca: Ti: Pr takes by weighing each preparation of raw material admixtion at 1: 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is placed in the alumina crucible, places high-temperature electric resistance furnace to be warming up to 1200 ± 10 ℃ with 10 ℃/min, in air, be incubated 2～3 hours, obtain fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, place in the alumina crucible, put into the corundum ceramic pipe of sealing, feeding overall flow rate is the pure H of 100ml/min
2Gas, being warming up to 850 ℃ of insulations with 10 ℃/min handled 6 hours, cooling back acquisition fluorescence powder is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got pure H after the oven dry material sieves
2The CaTiO of atmosphere aftertreatment
3: the 0.002Pr fluorescent material.
Embodiment 22
With chemical pure or analytical pure lime carbonate CaCO
3, titanium dioxide TiO
2, hydroxide Al (OH
3)
3With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio is that Ca: Ti: Pr: Al is 1: 1: 0.002: 0.25 takes by weighing each preparation of raw material admixtion, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material takes by weighing by every part of 5g, depress to the disk of Φ 22mm * 3mm in the 150MPa uniaxial compression, disk is put in the corundum crucible, places high-temperature electric resistance furnace to be warming up to 1200 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then with the fluorescent material grind into powder, putting into the carbon box of sealing handled 6 hours in 800 ℃ of insulations, the fluorescence powder that obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got the CaTiO of CO reducing atmosphere anneal after the oven dry material sieves
3: 0.002Pr, 0.25Al phosphor material powder.
Embodiment 23
With chemical pure or analytical pure hexanaphthene, polyoxyethylene glycol Octyl Ether, praseodymium nitrate Pr (NO
3)
3, strontium nitrate Sr (NO
3)
2, butyl (tetra) titanate, aluminum nitrate Al (NO
3)
3With methyl ethyl diketone be raw material, be 1: 1: 0.002 by Sr: Ti: Pr: Al: 0.25 takes by weighing each preparation of raw material admixtion.Earlier with praseodymium nitrate Pr (NO
3)
3Be dissolved in the 100ml beaker, add appropriate amount of deionized water and be heated to dissolving fully, adjusting PH is 4～5, and solution Pr ionic concn is decided to be 1.0mol/L.Add the 100ml hexanaphthene, agitation condition adds 20ml surfactant polyethylene Octyl Ether down, adds then by proportioning and mixes 5ml Pr (NO
3)
3Solution and an amount of Sr (NO
3)
2With Al (NO
3)
3Solution, add again a spot of primary isoamyl alcohol to solution transparent till, continue to stir 30 minutes.Adding butyl (tetra) titanate is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel of homogeneous transparent at last, gel is placed 100 ℃ of dryings, dried xerogel takes out to grind and obtains burning till the wet-mixed material of usefulness, and compound places in the alumina crucible, places high-temperature electric resistance furnace to be warming up to 1050 ℃ with 10 ℃/min, insulation is 3 hours in air, obtains the fluorescent material without the reducing atmosphere aftertreatment.Then, put into the corundum ceramic pipe of sealing, feed pure H the fluorescent material grind into powder
2Gas, flow velocity is 100ml/min, handled 6 hours in 800 ℃ of insulations, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got the SrTiO of pure H2 atmosphere anneal after the oven dry material sieves
3: 0.002Pr, 0.25Al phosphor material powder.
Embodiment 24
With chemical pure or analytical pure hexanaphthene, polyoxyethylene glycol Octyl Ether, praseodymium nitrate Pr (NO
3)
3, strontium nitrate Sr (NO
3)
2, butyl (tetra) titanate, aluminum nitrate Al (NO
3)
3With methyl ethyl diketone be raw material, be 1: 1: 0.002 by Sr: Ti: Pr: Al: 0.25 takes by weighing each preparation of raw material admixtion.Earlier with praseodymium nitrate Pr (NO
3)
3Be dissolved in the 100ml beaker, add appropriate amount of deionized water and be heated to dissolving fully, adjusting pH is 4～5, and solution Pr ionic concn is decided to be 1.0mol/L.Add the 100ml hexanaphthene, agitation condition adds 20ml surfactant polyethylene Octyl Ether down, adds then by proportioning and mixes 5ml Pr (NO
3)
3Solution and an amount of Sr (NO
3)
2With Al (NO
3)
3Solution, add again a spot of primary isoamyl alcohol to solution transparent till, continue to stir 30 minutes.Adding butyl (tetra) titanate is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel of homogeneous transparent at last, gel is placed 100 ℃ of dryings, dried xerogel takes out to grind and obtains burning till the wet-mixed material of usefulness, place high-temperature electric resistance furnace to be warming up to 1050 ℃, in air, be incubated 2～3 hours, obtain fluorescent material without the reducing atmosphere aftertreatment with 10 ℃/min.Then with the fluorescent material grind into powder, put into plumbago crucible, handled 6 hours in 800 ℃ of insulations, the fluorescence powder that the cooling back obtains is 1: 1.5 adding dehydrated alcohol by the weight ratio of fluorescence powder and dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got the SrTiO of CO atmosphere anneal after the oven dry material sieves
3: 0.002Pr, 0.25Al phosphor material powder.
Claims (8)
1. the preparation method of a high brightness red alkaline earth titanate fluorescent powder is characterized in that: may further comprise the steps:
1) preparation of solid phase batch mixing method or wet-chemical reaction method is burnt till and is used compound, and the prescription composition formula is: ATiO
3: xRe, yM; Wherein A is a kind of of alkaline earths Ca, Sr, Ba element, promptly with CaTiO
3, SrTiO
3Or BaTiO
3Alkaline earth titanate is a luminous host; Re is a Doped Rare Earth luminescence center ion, is praseodymium Pr; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more;
2) high temperature reduction atmosphere firing process or reducing atmosphere aftertreatment technology burn till processing to burning till with compound, obtain to burn till the fluorescence powder;
3) be 1: 0.5～2.5 adding dehydrated alcohols by the weight ratio of burning till fluorescence powder and dehydrated alcohol, at rotating speed is that ball milling mixes 4～24h in 50～250r/min planetary ball mill, the ball milling material was dried 6～24 hours in 50～150 ℃ of baking ovens, after oven dry material sieves promptly.
2. preparation method according to claim 1 is characterized in that: described solid phase batch mixing method is: the compound with alkaline earth carbonate, titanium dioxide, rare earth nitrate, supplementary doping element M is a raw material, is ATiO by atomic ratio
3: xRe, yM take by weighing each raw material, and wherein A is Ca, Sr or Ba, and Re is a Doped Rare Earth luminescence center ion, is praseodymium Pr; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more; Weight ratio by raw material and deionized water is 1: 0.5～1.5, adds deionized water, and ball milling mixes 2～36h in rotating speed 200r/min planetary ball mill, and the ball milling material was dried 6～36 hours in 50～150 ℃ of baking ovens, promptly got to burn till to use compound.
3. preparation method according to claim 1, it is characterized in that: described wet-chemical reaction method is: adopting the compound of alkaline earth nitrate, butyl (tetra) titanate, rare earth nitrate and supplementary doping element M is raw material, and is assistant chemical reagent with hexanaphthene, polyoxyethylene glycol Octyl Ether and methyl ethyl diketone; By atomic ratio is ATiO
3: xRe, yM take by weighing each raw material, and wherein A is Ca, Sr or Ba, and Re is a Doped Rare Earth luminescence center ion, is praseodymium Pr; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more; The rare earth nitrate raw material is added appropriate amount of deionized water, and being mixed with rare earth ion concentration is that 0.5～2.0mol/L, pH are 2～6 rare earth nitrate solution; Get 50～150ml hexanaphthene, agitation condition adds 10～50ml surfactant polyethylene Octyl Ether down, add the nitric acid diluent of pressing atom proportioning blended rare earth nitrate solution 2～10ml, alkaline earth nitrate solution and supplementary doping element compound then, add again primary isoamyl alcohol to solution transparent till, continue to stir 10～60 minutes; The butyl (tetra) titanate raw material that adds again by the proportioning weighing is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gelinite of homogeneous transparent at last, it 50～250 ℃ of dryings, is promptly got to burn till after the exsiccant xerogel grinds and use compound.
4. preparation method according to claim 2 is characterized in that: the alkaline earth carbonate in the described solid phase batch mixing method is CaCO
3, SrCO
3Or BaCO
3In one or more.
5. preparation method according to claim 3 is characterized in that: the alkaline earth nitrate in the described wet-chemical reaction method is Ca (NO
3)
2, Sr (NO
3)
2Or Ba (NO
3)
2In one or more.
6. according to claim 2 or 3 described preparation methods, it is characterized in that: the compound of described supplementary doping element M is oxide compound, oxyhydroxide or the carbonate cpds of supplementary doping element M.
7. preparation method according to claim 1 is characterized in that: described high temperature reduction atmosphere firing process is: will burn till plumbago crucible or the corundum matter tube furnace of directly putting into favorable sealing property with compound, logical CO, N
2, H
2Or NH
3In a kind of gas or its mixed gas, begin to be warming up to 800～1400 ℃ from room temperature with 10 ℃/min, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, after insulation finishes, keep the reducing atmosphere furnace cooling to obtain to burn till the fluorescence powder to room temperature.
8. preparation method according to claim 1, it is characterized in that: described reducing atmosphere aftertreatment technology is: will burn till with compound and put into high-temperature electric resistance furnace, begin to be warming up to 1000～1400 ℃ from room temperature with 10 ℃/min, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, insulation finishes the back furnace cooling and obtains fluorescent material; Then fluorescent material is put into the plumbago crucible or the corundum matter tube furnace of favorable sealing property, logical CO, N
2, H
2Or NH
3In a kind of gas or its mixed gas, begin to be warming up to 600～1100 ℃ from room temperature with 10 ℃/min, carried out sufficient reducing atmosphere aftertreatment reaction in 2～10 hours in the post-processing temperature insulation of setting, insulation finishes the back and keeps the reducing atmosphere furnace cooling to obtain to burn till the fluorescence powder to room temperature.
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| CN101619211B (en) * | 2009-07-10 | 2012-11-07 | 东华大学 | A Ca1-x-yTiO3: eu3+x, sm3+yphosphor and its preparation method |
| CN101775288B (en) * | 2009-11-13 | 2012-12-05 | 东华大学 | Ca1-x-yTiO3: Eu<3+>x, Y<3+>y fluorescent powder and preparation method thereof |
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| CN102660280B (en) * | 2012-05-23 | 2013-12-25 | 南京工业大学 | Titanate red phosphor for white light-emitting diode (LED) and preparation method for titanate red phosphor |
| CN105623659B (en) * | 2016-01-25 | 2018-04-13 | 深圳市聚飞光电股份有限公司 | A kind of preparation method of LED titanate fluorescent powders |
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