CN100406536C - Novel rare earth three-based colour fluorescence powder and preparation process thereof - Google Patents
Novel rare earth three-based colour fluorescence powder and preparation process thereof Download PDFInfo
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- CN100406536C CN100406536C CNB2005100266171A CN200510026617A CN100406536C CN 100406536 C CN100406536 C CN 100406536C CN B2005100266171 A CNB2005100266171 A CN B2005100266171A CN 200510026617 A CN200510026617 A CN 200510026617A CN 100406536 C CN100406536 C CN 100406536C
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Abstract
The present invention discloses a rare-earth tricolor fluorescent powder. The composition of the present invention is represented by a general formula La2 O3: xRE, wherein RE represents rare earth doping ion praseodymium Pr, neodymium Nd, europium Eu and terbium Tb, and x=0.001-0.1. The present invention also discloses a liquid phase mixture-high temperature solid phase method for preparing the rare-earth tricolor fluorescent material. The rare-earth tricolor fluorescent powder can be excited by 250 nm-300 nm ultraviolet light and can respectively emit red, green and blue light, and the green light has optimal effect; besides, La2O3: RE (RE=Pr, Eu, Tb, Nd) has similar excitation spectrums. Therefore, the rare-earth tricolor fluorescent powder which can be used for exciting a quasi-molecule discharging light source can be used for developing a novel green energy-saving no-mercury fluorescent lamp or used for RED fluorescent powder. By the method, lanthanum oxide and rare earth doping ions can be fully dispersed and contacted in a solution, reactants are uniformly mixed, and the component distribution of the prepared fluorescent powder is uniform; besides, the fluorescent powder having small granularity and favorable lighting effect can be prepared.
Description
Technical field
The present invention relates to luminescent material of a kind of burst of ultraviolel and preparation method thereof, a kind of specifically is that quasi-molecule light source activation and RED show the novel rare earth three-based colour fluorescence powder of usefulness and the preparation method of this fluorescent material.
Background technology
Energy-conservation and environmental protection is the two principal themes of green illumination.Present widely used electricity-saving lamp light efficiency is about 701m/w, fluorescent material needs mercuryvapour as working gas, therefore the mercury pollution environment researchs and develops novel, eco-friendly energy-saving illumination technology and corresponding luminescent material has become an important research direction of development of new non-mercury florescent lamp in recent years.Excimer light source has its unique advantage, and as working under barometric point, owing to there is not the radiating self-absorption, luminous efficiency is very high, can reach 50%～80%, and high power density (＞1MW/cm is arranged
3), the micro discharge channels time length is the ns magnitude, it is capable of fast starting to discharge, and also can make the head light of different shape as required.And its emission narrow-band spectrum, emission wavelength spreads all over can see vacuum ultraviolet, is considered to extremely rising lighting source of new generation.The key of exploitation quasi-molecule discharge florescent lamp is that the three primary colors fluorescent powder that excites of research respective wavelength is (as XeBr
*, Br
2 2The emission wavelength of quasi-molecule discharge be respectively 282 and 289nm).On the other hand, RED flat pannel display and luminescent material thereof also are the important goals of studying at present.
The patent documentation of luminescent material open aspect, early stage just like the disclosed green-fluorescent powder for lamp of Chinese patent publication number CN1104235A, it is to be raw material with relevant rare earth oxide and Secondary ammonium phosphate, adds an amount of active SiO
2, H
3BO
3And Li
2CO
3, through high temperature solid state reaction, the fluor of transmitting green fluorescence under the preparation ultraviolet laser, the chemical formula of this fluor is: (La
1-X-Y-ZCe
XTb
Y)
2O
3(1-m-n) P
2O
5ZLiOmSiO
2NB
2O
3
As the Chinese patent publication number is the disclosed compound based on RE phosphate of CN1146478A as the twinkler in the plasma system, its said compound is that mix at least a kind of general formula of rare earth element is LnPO
4Phosphoric acid salt, wherein Ln is yttrium, lanthanum, gadolinium or lutetium, its rear-earth-doped element is the mixture of terbium and cerium.
As the Chinese patent publication number is the manufacture method of the disclosed a kind of blue colour fluorescent powder of CN1190115A, and the chemical expression of this fluorescent material is BaMgAl14O23:Eu.
As the Chinese patent publication number be the disclosed compound based on the lanthanum orthophosphate that contains thulium of CN1278855A in plasma body or x-ray system as the purposes of fluorescent material, it also contains gadolinium in lanthanum orthophosphate.
As the Chinese patent publication number is the disclosed a kind of efficient green phosphor of rare-earth phosphate of CN1276406, and its chemical constitution is: (Ln
1-X-Y-ZTb
XR
YLi
Z) [(1-m) PO
4MBO
3].Ln is Y in the formula, La, Gd and Lu; R is Ce, Pr, Dy rare earth element.
As the Chinese patent publication number is disclosed a kind of borate red fluorescent powder for color plasma plate display of CN1408812A and manufacture method thereof, and the chemical formula of its fluorescent material is (Y
1-X-Y-ZGd
ZM
YEu
X) BO
3, M is one or several among La, Tb, the Sm.
As the Chinese patent publication number is the disclosed rareearth blue fluorescent material of CN1483788, Preparation Method And The Use, and the general formula of this kind rareearth blue fluorescent material is: (M1)
x(M2)
yEu
z(M3)
w(SiO
3)
nCl
mSiO
2, M1 is the alkali metal that is selected from sodium, potassium, rubidium or its combination in the formula, and M2 is the alkali earth metal that is selected from magnesium, calcium, strontium, barium or its combination, and M3 is selected from the thulium of yttrium, lanthanum, terbium, cerium or its combination.
As the Chinese patent publication number is the disclosed a kind of rare-earth activated Y of CN1580183A
2SiO
5Fluorescent material and its production and application, this fluorescent material is made up of yttrium oxide or Yttrium trinitrate, silicon-dioxide, lanthanide oxide or nitrate, and described lanthanide series compound is cerium oxide, europium sesquioxide or terbium sesquioxide, and nitrate is cerous nitrate, europium nitrate or Terbium trinitrate.This kind fluorescent material matrix is Y
2SiO
5The high temperature phase, fluorescent material is Y
2SiO
5: Tb, Y
2SiO
5: Ce, Tb, Y
2SiO
5: Ce or Y
2SiO
5: Eu.
Aspect luminescent material foreign patent document, open the patent of the manufacture method of the relevant rare-earth phosphate phosphor of flat 6-128565 (in May, 1994) just like Japanese kokai publication hei 5-171143 (in July, 1993) and spy in addition.
A kind of chemical formula of U.S. Pat P6097146 report is (Y
1-a-bGd
aEu
b)
2O
3Novel yttrium europium oxide gadolinium rouge and powder.
A kind of chemical formula of U.S. Pat P6042747 report is (Y
1-a-b-CGd
CM
bEu
a) BO
3Novel borate rouge and powder.
Alkali metal aluminosilicate fluorescent material that a kind of europium of U.S. Pat P3897359 report excites and preparation method thereof, the chemical constitution formula of this fluorescent material is (Ca
xSr
yBa
zEu
p) O
X+y+z+pAl
2O
32SiO
2, its emission spectrographic wavelength region may under the exciting of the ultraviolet ray of 200-380nm or electron beam is that the near ultraviolet region arrives blue white area.
For above-mentioned fluorescent material, have plenty of and adopt the high temperature solid-state reduction method to prepare.
Exactly an amount of various rare earth oxides are dissolved in nitric acid as the disclosed green-fluorescent powder for lamp of Chinese patent publication number CN1104235A, regulate pH value then, add oxalic acid and generate oxalate coprecipitation, add H again
3BO
3, active SiO
2And Li
2CO
3, 600 ℃ of following calcinations 1～3 hour, again with the reaction of 85% phosphoric acid and firing product, the calcination in 1200～1400 ℃ and weakly reducing atmosphere of dry back.Products therefrom was through 700～800 ℃ of thermal treatments 10 minutes.
Be the disclosed compound based on RE phosphate of CN1146478A as the twinkler in the plasma system still be that throw out is calcined under 900～1200 ℃ and reducing atmosphere as the Chinese patent publication number.
For another example the Chinese patent publication number be the disclosed compound based on the lanthanum orthophosphate that contains thulium of CN1278855A in plasma body or x-ray system as the purposes of fluorescent material, it also is with the temperature lower calcination of phosphoric acid salt at least 1000 ℃.
And for example the Chinese patent publication number is the disclosed a kind of efficient green phosphor of rare-earth phosphate of CN1276406, its preparation method is to take by weighing corresponding rare earth oxide and phosphoric acid salt, the salt that contains lithium, boride thorough mixing mill is even, at first after 700～950 ℃ of pre-burning 0.5-3 hours, it is even to take out mill, carries out the calcination second time at 1050～1350 ℃ again, about 1-3 hour.This process is carried out in weakly reducing atmosphere.
Again also as the Chinese patent publication number be that the preparation method of the disclosed a kind of borate red fluorescent powder for color plasma plate display of CN1408812A is exactly that first proportioning according to chemical formula takes by weighing required rare-earth oxide: lanthanum trioxide (La
2O
3), terbium sesquioxide (Tb
4O
7), Samarium trioxide (Sm
2O
3) in one or more yttrium oxide (Y
2O
3), gadolinium sesquioxide (Gd
2O
3) and europium sesquioxide (Eu
2O
3) be dissolved in nitric acid or the hydrochloric acid, form rare earth metal salt solutions, under the condition of heating, oxalic acid or the carbonate solution for preparing joined rare earth metal salt solutions then, obtain the oxalate or the carbonate sediment of rare earth metal.Behind the oxalate or carbonate sediment oven dry with rare earth metal, obtain the rare-earth oxide mixture after 0.5-2 hour again 800～1200 ℃ of insulations.After at last rare-earth oxide mixture and boric acid, fusing assistant and agate ball being mixed together evenly, under 1100～1450 ℃ of temperature condition, calcining and obtain borate rouge and powder.
A kind of chemical formula of U.S. Pat P6097146 report is (Y for another example again
1-a-bGd
aEu
b)
2O
3Novel yttrium europium oxide gadolinium rouge and powder also is to adopt the high-temperature solid phase reaction method synthetic, and it is to take by weighing Y earlier
2O
3, Gd
2O
3, Eu
2O
3, behind the nitric acid dissolve, add the oxalic acid solution precipitation, obtain rare-earth oxide at 1000 ℃ of pyrolytic decompositions, behind the adding solubility promoter mixing, 1400 ℃ of high-temperature roastings obtain yttrium europium oxide gadolinium rouge and powder.
The main drawback that adopts the high temperature solid-state reduction method to obtain rare-earth luminescent material is the energy consumption height, the cost height.Thereby in high-temperature sintering process, introduce the impurity influence simultaneously easily and make the photochromism of fluorescent material, and the fluorescent material that makes is difficult to the fluorescent material that further processing obtains fine sizes.
Adopting at present sol-gel method to prepare rare-earth luminescent material in addition, is (Y as a kind of chemical formula of U.S. Pat P6042747 report
1-a-b-CGd
CM
bEu
a) BO
3Novel borate rouge and powder is exactly like this.
Be the disclosed a kind of rare-earth activated Y of CN1580183A also as the Chinese patent publication number
2SiO
5Fluorescent material, its preparation method also is so, be in heated and stirred equipment, yttrium oxide and lanthanide rare compound are dissolved in hot concentrated in, the back that reacts completely adds the silicone grease compounds, the pH value 4～8 of regulator solution leaves standstill for some time formation gel under 60～100 ℃ of constant temperature; Gel heats for some time and obtains solid product under 300～600 ℃ of conditions; After solid product ground, in 400～1000 ℃ of scopes, calcination in the reducing atmosphere was ground after the calcination again, adds one or more inorganic salt, in 800～1600 ℃ of scopes, and calcination once more in the reducing atmosphere, cooling is taken out dilute acid wash and is obtained rare-earth activated Y
2SiO
5Fluorescent material.
And for example the Chinese patent publication number is that the preparation method of the disclosed rareearth blue fluorescent material of CN1483788 still is so, it adopts two kinds of methods to prepare colloidal sol, a kind of is with water-soluble alkali metal salts and excessive hydrochloric acid, after stirring, in mixing solutions, add the capacity tetraalkyl orthosilicate again, stir until the colloidal sol that forms homogeneous transparent.Another kind method is with water-soluble alkali metal salts and excessive hydrochloric acid, after stirring, and remix capacity tetraalkyl orthosilicate and hydrochloric acid, the mixing solutions with water-soluble alkali metal salts and excessive hydrochloric acid after the stirring hydrolysis adds, and stirs until the colloidal sol that forms homogeneous transparent.The pH value of gained vitreosol, mixes the back and adds excessive reductant and stirring to wherein adding alkaline earth salt and rare earth metal salt less than 7, leaves standstill and obtains wet gel.After the wet gel drying, under non-oxidizing atmosphere,, obtain rareearth blue fluorescent material in 500～800 ℃ of thermal treatments.
Though above-mentioned sol-gel method prepares rareearth blue fluorescent material, can under the condition of gentleness, carry out, greatly reduce sintering temperature, can make highly purified fluorescent material, avoided introducing the problem of impurity effectively owing to high sintering temperature, and each feed composition mixes more even, and the fluorescent material group that makes becomes to be more evenly distributed.But also exist the more complicated that operates, flow process is also dragged longly, and production cost is higher, the problem that production efficiency is low.
Aspect relevant rare-earth trichromatic fluorescent material, early stage report has Dutch Philips J.M.P.J.Verstegen can to roll up 1627 pages of disclosed being entitled as of 12 phases " light efficiency is 80 lumens/watt; colour rendering index is 85 of new generation luxury luminescent lamp " in 1974 121 by magazine (J.Electrochem.Soc) in U.S.'s electrochemistry, this technology adopts the synthetic method of rare-earth trichromatic powder, synthesizes (the Y that glows under different condition respectively
1Eu)
2O
3, (Ce.Tb) MgAl of green light
11O
19And (the Ba of blue light-emitting
1Eu) Mg
2Al
16O
27, then these three kinds of monochromatic powder are mixed and made into necessarily required fluorescent material by a certain percentage.
Reaching the Chinese patent publication number is the preparation of the disclosed single-base double rare-earth-mixed fluorescent material with three basic colour of CN1135513A, and it is to mix Eu in the alkali-earth metal oxide hydrochlorate
3+And Tb
3+Obtain the fluorescence system of three kinds of emission coexistences through sintering.
Also reaching the Chinese patent publication number is the disclosed rare-earth trichromatic fluorescent material that is used for plant tissue culture of CN1311285A, it is by behind yttrium oxide rouge and powder, the green powder of cerium-zirconium aluminic and the barium magnesium aluminate blue powder uniform mixing and make, and in yttrium oxide rouge and powder and barium magnesium aluminate blue powder, be mixed with the activator europium in advance respectively, in the green powder of cerium-zirconium aluminic, be mixed with the activator terbium.Or by behind vanadium yttrium phosphate rouge and powder, yttrium oxide rouge and powder, fluogermanic acid magnesium rouge and powder, barium magnesium aluminate blue powder, strontium pyrophosphate purple light powder and the rare earth ultraviolet powder uniform mixing and make, and in vanadium yttrium phosphate rouge and powder, yttrium oxide rouge and powder, fluogermanic acid magnesium rouge and powder, barium magnesium aluminate blue powder and strontium pyrophosphate purple light powder, be mixed with the activator europium in advance respectively, in fluogermanic acid magnesium rouge and powder, be mixed with activator manganese.
Reach the preparation method that the Chinese patent publication number is the disclosed rare earth luminescent material of CN1338501A again, the theory that it is based on " electronic configuration has a pair of rare earth ion of conjugacy; can realize transfer transport under certain condition and produce the valence state ANOMALOUS VARIATIONS ", boron calcium phosphate and cerium (Ce) sensitization system, boron aluminium calcium phosphate and cerium (Ce) sensitization system thereof, chlorine oxygen lime borate and cerium (Ce) the sensitization system thereof of selecting rare-earth europium (Eu) and terbium (Tb) to mix altogether, and will obtain the rare-earth trichromatic fluor of three kinds of emission wavelength coexistences behind three's mixed sintering.
Also reaching the Chinese patent publication number again is the disclosed alkali metal stannate phosphate base of CN1603385A luminescent material and preparation method thereof, and its matrix chemical constitution formula is MSn
3P
3O
11+xWherein M is sodium and potassium, adulterated alkali metal stannate phosphoric acid salt luminescent material, and its chemical constitution formula is MSn
3P
3O
11+x: R, R are Doped Rare Earth and elements such as manganese, gallium, and doping is below 20% of amount of substance of tin.
Summary of the invention
It is good to an object of the present invention is to provide a kind of good stability and luminous intensity, excites and be used for the rare-earth trichromatic fluorescent powder of green energy conservation non-mercury florescent lamp or RED demonstration as the quasi-molecule charging source.
Another object of the present invention provides a kind of preparation method of rare-earth trichromatic fluorescent powder, and this method can make the rare-earth trichromatic fluorescent powder that obtains that further raising is being arranged aspect uniformity coefficient and the illumination effect.
Purpose of the present invention can be achieved through the following technical solutions.
The invention provides a kind of rare-earth trichromatic fluorescent powder, its composition is represented by following general formula: La
2O
3: xRE, wherein RE is rear-earth-doped ion praseodymium Pr, neodymium Nd, europium Eu, terbium Tb, x=0.001～0.1.
The present invention also provides a kind of method for preparing rare-earth trichromatic fluorescent powder, and this method has following steps:
1, be equipped with liquid phase in order to the below legal system:
The lanthanum trioxide of mixed chemical calculated amount and rare earth nitrate solution also grind, and be during grinding that solid particulate is levigate as much as possible, presents uniform slurry to solution, liquid phase, described rare earth is praseodymium Pr, neodymium Nd, europium Eu or terbium Tb;
2, with after the liquid phase oven dry, regrinding with the sample that mixes, in confined conditions in 800～1300 ℃ of thermal treatments 2～4 hours, treats that temperature reduces to room temperature after the grinding, obtains rare-earth trichromatic fluorescent powder.
In a better example of the present invention, rare earth nitrate solution is selected the rare earth nitrate ethanolic soln or the aqueous solution for use.
The rare-earth trichromatic fluorescent powder that the present invention is prepared is as molecular formula La
2O
3: RE (RE=Pr, Nd, Eu, Tb).Use lanthanum trioxide as matrix, rear-earth-doped ion is as luminescent activator, because rare earth ion radius and chemical property are very approaching, therefore rear-earth-doped ion can enter in the lanthanum trioxide lattice well.In this system, rear-earth-doped ion can send the characteristic spectrum of different colours separately as luminescent activator.As La
2O
3: the strong absorption band of Pr and can both produce the green glow (as shown in Figure 2) of very strong 510nm in this exciting light scope in 250～300nm scope.La
2O
3: the excitation spectrum of Nd 250 and 308nm near two contour substantially peaks have appearred, excite with these two wavelength to obtain similar broadband emission peak, the strongest emission wavelength is the blue light (as shown in Figure 3) of 460nm.La
2O
3: Eu and La
2O
3: the absorption spectrum of Tb and La
2O
3: the Pr comparing class seemingly, strong absorption band and inspires Eu and Tb feature emission peak separately in 250～300nm scope, its emission peak all be sharp line spectra (being respectively ruddiness and green glow), is that (as Fig. 4, shown in 5) launched in the 4f-4f transition of electron of rare earth ion.
Liquid-phase mixing-high temperature solid-state method that the present invention adopts, its notable attribute is that lanthanum trioxide fully disperses to contact in solution with rear-earth-doped ion, oven dry then, grind, it is more even that reactant is mixed, the fluorescent material composition that makes is more evenly distributed, and it is finer to make granularity, the better fluorescent material of illumination effect.
Rare-earth trichromatic fluorescent powder of the present invention can be sent red, green, blue three coloured light respectively, especially the green glow best results by the 250-300nm ultraviolet excitation.And La
2O
3: (Tb Nd) has similar excitation spectrum to RE for RE=Pr, Eu.Therefore, the three primary colors fluorescent powder that can excite as the quasi-molecule charging source of the present invention is used for development of new green energy conservation non-mercury florescent lamp or is used for RED fluorescent material.
Description of drawings
Fig. 1 is the La of illustrative example of the present invention
2O
3: the XRD figure of RE;
Fig. 2 is the La of illustrative example of the present invention
2O
3: the fluorescence spectrum figure of Pr;
Fig. 3 is the La of illustrative example of the present invention
2O
3: the fluorescence spectrum figure of Nd;
Fig. 4 is the La of illustrative example of the present invention
2O
3: the fluorescence spectrum figure of Eu;
Fig. 5 is the La of illustrative example of the present invention
2O
3: the fluorescence spectrum figure of Tb;
Embodiment
A kind of rare-earth trichromatic fluorescent powder, its composition is represented by following general formula: La
2O
3: xRE, wherein RE is rear-earth-doped ion praseodymium Pr, neodymium Nd, europium Eu, terbium Tb, mol ratio x=0.001～0.1.
In rare-earth trichromatic fluorescent powder of the present invention, use lanthanum trioxide as matrix, rear-earth-doped ion is as luminescent activator, because rare earth ion radius and chemical property are very approaching, therefore rear-earth-doped ion can enter in the lanthanum trioxide lattice well, and the fluorescence property of this fluorescent material can be kept well.
Rare-earth trichromatic fluorescent powder of the present invention makes with aforesaid liquid-phase mixing-high temperature solid-state method, makes lanthanum trioxide and rear-earth-doped ion fully disperse to contact in solution, and it is more even that reactant is mixed.Solve existing high temperature solid-state reduction method and obtained the energy consumption height that rare-earth luminescent material exists, the problem that cost is high.Solved sol-gel method simultaneously and existed the more complicated that operates, flow process is also dragged longly, and production cost is higher, the problem that production efficiency is low.
In preparation method of the present invention, the solvent of employing is selected ethanol or water for use, and rare earth nitrate solution is selected the rare earth nitrate ethanolic soln or the aqueous solution for use.But be not limited thereto, as long as the solvent of selecting can dissolve rare earth nitrate, can not have a negative impact to the luminescent properties of the rare-earth trichromatic fluorescent powder of gained gets final product, and this is accomplished than being easier to for a person skilled in the art.
In preparation method of the present invention, the time of grinding is well known to those skilled in the art, is generally 5～10 minutes.In the inventive method, the temperature of liquid phase oven dry also is well known to those skilled in the art, is generally 60～200 ℃, and the time is controlled as required.Carry out in confined conditions for high temperature sintering, air tight condition also is well known to those skilled in the art.
Further specify the present invention by the following examples, but should be understood that these embodiment are exemplary, the present invention does not limit to this.
Embodiment 1
With 1.629g La
2O
3Pr (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 2
With 1.629g La
2O
3Nd (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 3
With 1.629g La
2O
3Eu (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 4
With 1.629g La
2O
3Tb (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 5
With 1.629g La
2O
3Pr (NO with 5mL 0.01mol/L
3)
3Aqueous solution is even, grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 6
With 1.629g La
2O
3Nd (NO with 5mL 0.01mol/L
3)
3Aqueous solution is even, grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 7
With 1.629g La
2O
3Eu (NO with 5mL 0.01mol/L
3)
3Aqueous solution is even, grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 8
With 1.629g La
2O
3Tb (NO with 5mL 0.01mol/L
3)
3Aqueous solution is even, grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 9
With 1.629g La
2O
3Pr (NO with 1mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 3 hours in 1200 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 10
With 1.629g La
2O
3Pr (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 2 hours in 1300 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 11
With 1.629g La
2O
3Pr (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 4 hours in 800 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Embodiment 12
With 1.629g La
2O
3Pr (NO with 5mL 0.01mol/L
3)
3Ethanolic soln mixes, and grinds five minutes, and solid particulate is levigate as far as possible, presents uniform slurry to solution.Oven dry, and then grind is placed at the sample that mixes in the retort furnace, handles 4 hours in 1000 ℃ in confined conditions, treats that temperature reduces to room temperature, promptly obtains product.
Claims (3)
1. rare-earth trichromatic fluorescent powder, its composition is represented by following general formula: La
2O
3: xRE, wherein RE is rear-earth-doped ion praseodymium Pr, neodymium Nd, europium Eu or terbium Tb, mol ratio x=0.001～0.1.
2. method for preparing the described rare-earth trichromatic fluorescent powder of claim 1, this method has following steps:
[1], be equipped with liquid phase in order to the below legal system:
The lanthanum trioxide of mixed chemical calculated amount and rare earth nitrate solution also grind, and be during grinding that solid particulate is levigate as much as possible, presents uniform slurry to solution, liquid phase, described rare earth is praseodymium Pr, neodymium Nd, europium Eu or terbium Tb;
[2], with after the liquid phase oven dry, regrinding with the sample that mixes, in confined conditions in 800～1300 ℃ of thermal treatments 2～4 hours, treats that temperature reduces to room temperature after the grinding, obtains rare-earth trichromatic fluorescent powder.
3. method as claimed in claim 2 is characterized in that: described rare earth nitrate solution is selected the rare earth nitrate ethanolic soln or the aqueous solution for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100266171A CN100406536C (en) | 2005-06-09 | 2005-06-09 | Novel rare earth three-based colour fluorescence powder and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100266171A CN100406536C (en) | 2005-06-09 | 2005-06-09 | Novel rare earth three-based colour fluorescence powder and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1693417A CN1693417A (en) | 2005-11-09 |
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| CN101435762B (en) * | 2008-12-09 | 2012-08-22 | 彩虹集团电子股份有限公司 | Method for testing dispersed characteristic of fluorescent powder insoluble to water |
| FR2952074B1 (en) * | 2009-11-03 | 2013-08-02 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF MONOCRYSTALLINE CUBIC SESQUIOXIDES AND THEIR APPLICATIONS |
| CN101982582B (en) * | 2010-08-24 | 2012-06-20 | 浙江理工大学 | Submicron green fluorescence fiber La2O3:Tb3+ electrostatic spinning method |
| FR3008995B1 (en) * | 2013-07-24 | 2016-12-09 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF MONOCRYSTALLINE CUBIC SESQUIOXIDES AND APPLICATIONS |
| CN108239335A (en) * | 2016-12-23 | 2018-07-03 | 新加坡国立大学 | Plastic matrix with luminosity and preparation method thereof |
| CN113402744B (en) * | 2021-05-06 | 2022-11-08 | 甘肃颐年聚光科技有限责任公司 | Light conversion film capable of promoting plant growth and preparation method and application thereof |
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| US4798768A (en) * | 1986-10-08 | 1989-01-17 | U.S. Philips Corporation | Luminescent alumino-silicate and/or alumino-borate glass comprising lanthanum and/or gadolinium and luminescent screen provided with such a glass |
| JPH09255953A (en) * | 1996-03-27 | 1997-09-30 | Futaba Corp | Phosphor and preparation thereof |
| US6097146A (en) * | 1997-01-14 | 2000-08-01 | Kabushiki Kaisha Toshiba | Phosphor for plasma display panel |
| CN1378227A (en) * | 2002-01-18 | 2002-11-06 | 叶峰 | Double layer coating method for rare-earth trichromatic energy saving fluorescent lamp |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4798768A (en) * | 1986-10-08 | 1989-01-17 | U.S. Philips Corporation | Luminescent alumino-silicate and/or alumino-borate glass comprising lanthanum and/or gadolinium and luminescent screen provided with such a glass |
| JPH09255953A (en) * | 1996-03-27 | 1997-09-30 | Futaba Corp | Phosphor and preparation thereof |
| US6097146A (en) * | 1997-01-14 | 2000-08-01 | Kabushiki Kaisha Toshiba | Phosphor for plasma display panel |
| CN1378227A (en) * | 2002-01-18 | 2002-11-06 | 叶峰 | Double layer coating method for rare-earth trichromatic energy saving fluorescent lamp |
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