CN1297964A - Preparation of red phosphor - Google Patents

Preparation of red phosphor Download PDF

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CN1297964A
CN1297964A CN 99124180 CN99124180A CN1297964A CN 1297964 A CN1297964 A CN 1297964A CN 99124180 CN99124180 CN 99124180 CN 99124180 A CN99124180 A CN 99124180A CN 1297964 A CN1297964 A CN 1297964A
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preparation
oxalate
red fluorescence
rare
feature
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CN1105153C (en
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贾积晓
王振华
张德源
何晓华
黄鹰
翁楚豪
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Yaolong Non-Ferrous Metal Co Ltd Shanghai
Daiden Co Inc
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Yaolong Non-Ferrous Metal Co Ltd Shanghai
Daiden Co Inc
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Abstract

The present invention relates to one novel preparation process of red phosphor powder, and specifically the preparation process of red phosphor powder with the formula of (YAGdBEuC)BO3 and (YAGdBEuCMeX)BO3. The present invention aims at providing one improved technological process to make the red phosphor product have homogeneously distributed activator (Eu3+) density, complete crystal and thus obviously raised luminescing brightness and color purity.

Description

A kind of preparation method of red fluorescence powder
The present invention relates to a kind of preparation method of red fluorescence powder of novelty, being specifically related to a kind of structural formula is (Y AGd BEu C) BO 3With structural formula be (Y AGd BEu CMe W) BO 3The preparation method of red fluorescence powder.Red fluorescence powder of the present invention is mainly used among the plasma panel display PDP, and the used exciting light of fluorescent material of the present invention is the vacuum-ultraviolet light (VUV) of plasma generation.
The red fluorescence powder that is used for plasma panel display PDP at present mainly contains (YGdEu) 2O 3(YGdEu) BO 3Deng, (YGdEu) BO wherein 3Owing to having higher quantum yield under the exciting of vacuum-ultraviolet light, it is widely used.Prepared (YGdEu) BO in the past 3Method mainly be to make Y 2O 3, Gd 2O 3, Eu 2O 3With carry out high temperature solid state reaction after boric acid or boron oxide compound mix, the fluorescent material that obtains like this is because activator (Eu 3+) concentration distribution is inhomogeneous, thereby make the brightness of this fluorescent material not high.
The purpose of this invention is to provide a kind of improved processing method, make resulting fluorescent material because activator (Eu 3+) concentration distribution is more even, the fluorescent material crystallization is more complete, thereby has significantly improved the luminosity of powder, has improved purity of color.
Technical process of the present invention is as follows
Figure 9912418000051
Process characteristic of the present invention is as follows:
1. coprecipitation method prepares rare-earth oxalate:
The brightness that improves fluorescent material should make activator be evenly distributed, so the present invention adopts the Y that contains moisture, Eu, and rare earth element oxalate coprecipitation methods such as Gd make Eu 3+Ion is evenly distributed in the rare-earth oxalate (for example yttrium oxalate, gadolinium oxalate or yttrium oxalate gadolinium).Concrete operations are with yttrium, europium, and the oxide compound acid of gadolinium is molten, is made into certain density clear rare earth feed liquid.In another container, take by weighing oxalic acid, oxalic acid is dissolved in the deionized water.Oxalic acid solution is added above-mentioned rare earth feed liquid or rare earth feed liquid is added in the oxalic acid solution, stir to make and form the rare earth oxalate co-precipitation.With the oxalate coprecipitation that generated with the washed with de-ionized water of heat to pH=6-7 then solid-liquid separation to water content reach the requirement of regulation, standby.
2. make oxalate precipitation and excessive boric acid (solid) be mixed with fluorescent material of the present invention:
Ordinary oxide and boric acid batch mixing can produce the boric acid maldistribution, and finished product can produce the dephasign of oxide compound after the calcination, influences brightness.The method that the present invention adopts is that excessive boric acid is added in the oxalate precipitation, places in the mixing tank rolling batch mixing 3 hours.Because contain a large amount of moisture in the rare earth element oxalate, boric acid is dissolved in rare-earth oxalate particulate surface.After adding the boric acid of q.s, can make boric acid be evenly distributed on each rare-earth oxalate particulate surface through long batch mixing.With the calcination in the pyritous air atmosphere of mixed material, prepared sample is added entry and pellet shot from a slingshot, Ball milling, the 500 orders after scouring that sieves, oven dry, sieving on 200 order nylon wires and can obtaining purified structural formula with hexagonal lattice is (Y AGd BEu C) BO 3Red fluorescence powder of the present invention (for example yttrium borate europium gadolinium) crystal, and do not produce the oxide compound dephasign.The visible appended sem photograph of the particle diameter of product and particle dispersing property.
In the fluorescent material of said structure formula of the present invention if be mixed with small amount of N d 3+, Sm 3+, Dy 3+, Ca 2+Or Ba 2+In a kind of or several impurities ion, then can obtain structural formula is (Y AGd BEu CMe W) BO 3The higher red fluorescence powder of brightness of the present invention.
When Me represents Nd 3+, Sm 3+Or Dy 3+The time
W equals 0.001% (2A+2B+2C) to 0.5% (2A+2B+2C),
When Me represents Ca 2+Or Ba 2+The time
W equals 0.5% (2A+2B+2C) to 2% (2A+2B+2C);
The advantage of fluorescent material of the present invention is: high 5-20% is wanted in the brightness of the like product that its luminance factor is commercially available, and particle diameter is carefully to 1-10 μ m, and the dispersiveness of powder is good especially and make aftertreatment easy.
Specifically, structural formula of the present invention is (Y AGd BEu C) BO 3Red fluorescence powder prepare like this, it may further comprise the steps:
(a) mol ratio according to each material in the structural formula of following rare-earth oxalate takes by weighing yttrium oxide, europium sesquioxide; Or europium sesquioxide, gadolinium sesquioxide; Or yttrium oxide, europium sesquioxide, gadolinium sesquioxide; Make it be dissolved in an amount of concentrated hydrochloric acid (6N-12N) or nitric acid (6N-14N), be made into the rare earth feed liquid of clear, add oxalic acid and stirring by stoichiometry, making oxalate co-precipitation obtain structural formula is [(Y AGd BEu C) 2(C 2O 4) 3] rare-earth oxalate precipitation, the numerical value of A is 0-0.99 in the formula, is preferably 0.15-0.55; The numerical value of B is 0-0.99, is preferably 0.45-0.85; The numerical value of C is 0.01-0.20, is preferably 0.01-0.05; And must satisfy 0＜A+B≤0.99;
(b) with the above-mentioned rare-earth oxalate precipitation of hot wash, filter, solid-liquid separation, and sneak into excessive boric acid;
(c) in 700 ℃-1500 ℃ air atmosphere, after calcination 2-10 hour, obtain the yttrium borate europium, or boric acid europium gadolinium, or yttrium borate europium gadolinium fluorescent material;
(d) Ball milling, 500 orders sieve washing, the oven dry;
(e) on 200 order nylon wires, sieve again and can obtain product.
Structural formula of the present invention is (Y AGd BEu CMe W) BO 3Red fluorescence powder prepare like this, it may further comprise the steps:
(a) mol ratio according to each material in the structural formula of following rare-earth oxalate takes by weighing yttrium oxide, europium sesquioxide; Or europium sesquioxide, gadolinium sesquioxide; Or yttrium oxide, europium sesquioxide, gadolinium sesquioxide; Make it be dissolved in an amount of concentrated hydrochloric acid (6-12N) or nitric acid (6-14N), be made into the rare earth feed liquid of clear, and splash into therein and contain Nd 3+, Sm 3+, Dy 3+, Ca 2+Or Ba 2+In a kind of or several impurities ion solution, the described Nd that contains 3+, Sm 3+, Dy 3+, Ca 2+Or Ba 2+In a kind of or several impurities ion solution can be to contain impurity element Nd, Sm, Dy, the solution of the soluble compound of Ca or Ba, or with described impurity element Nd, Sm, Dy, the acid solution that the oxide compound of Ca or Ba is made into earlier.Add oxalic acid and stirring according to stoichiometry, making oxalate co-precipitation obtain structural formula is [(Y AGd BEu CMe W) 2(C 2O 4) 3] rare-earth oxalate precipitation, the numerical value of A is 0-0.99 in the formula, is preferably 0.15-0.55; The numerical value of B is 0-0.99, is preferably 0.45-0.85; The numerical value of C is 0.01-0.20, is preferably 0.01-0.1.And must satisfy 0＜A+B≤0.99;
When Me represents Nd 3+, Sm 3+Or Dy 3+The time
W equals 0.001% (2A+2B+2C) to 0.5% (2A+2B+2C),
When Me represents Ca 2+Or Ba 2+The time
W equals 0.5% (2A+2B+2C) to 2% (2A+2B+2C);
(b) with the above-mentioned rare-earth oxalate precipitation of hot wash, filter, solid-liquid separation, and sneak into excessive boric acid;
(c) in 700 ℃-1500 ℃ air atmosphere, after calcination 2-10 hour, obtain the yttrium borate europium, or boric acid europium gadolinium, or yttrium borate europium gadolinium fluorescent material;
(d) Ball milling, 500 orders sieve washing, the oven dry;
(e) on 200 order nylon wires, sieve again and can obtain product.
In the preparation process of the red fluorescence powder of above-mentioned two kinds of structural formulas of the present invention (b), the hot wash oxalate precipitation that is preferably 70-100 ℃ of usefulness is until PH=6-7; Described rare-earth oxalate precipitation also can comprise the moisture content (comprising crystal water, planar water or slurry free-water etc.) of 10-80% weight, comprises the moisture content of 20-50% weight preferably, better comprises the moisture content of 25-45% weight; Described boric acid and rare-earth oxalate middle-weight rare earths ionic mol ratio be necessary 〉=and 1; Described boric acid is the form batch mixing with solid boric acid, and mixing time is preferably 1-20 hour;
In the preparation process of the red fluorescence powder of above-mentioned two kinds of structural formulas of the present invention (c), the calcination temperature of described rare-earth oxalate precipitation and mebor is generally 700-1500 ℃, is preferably 1000-1200 ℃; The calcination mode of described rare-earth oxalate precipitation and mebor can be first 700-950 ℃ of pre-burning, again in 1000-1500 ℃ this burning, is preferably a calcination.
Fig. 1 is that the dispersion of particles of red fluorescence powder of the present invention is better as can be seen from Figure according to the sem photograph of the prepared red fluorescence powder of the present invention of method of embodiment 5 (amplifying 4800 times).
Fig. 2 is that the particle diameter of red fluorescence powder particle of the present invention as can be seen from Figure is thinner according to the sem photograph of the prepared red fluorescence powder of the present invention of method of embodiment 11 (amplifying 4800 times).
Below by embodiment and comparative example fluorescent material of the present invention is further described, all used raw materials of following embodiment of the present invention and comparative example all are commercially available available, all pre-burnings and this burning all are to carry out in air atmosphere, the used glass sphere of aftertreatment all is that diameter is the glass sphere of 1.5-3mm, and carries out Ball milling according to following part by weight:
Sample: moisture: glass sphere=1: 2: 1.5
Comparative example 1
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 gram, these three kinds of powder mixes evenly after, in 1 kilogram of this mixed powder, add 470 gram boric acid, after mixing in 3 hours, through 700 ℃ of pre-burnings 4 hours, 1150 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Comparative example 2
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid mixture of these three kinds of powder being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-10G ℃ is to pH=6-7.After 900 ℃ of coprecipitates burn till oxide compound, add 470 gram boric acid in 1 kilogram of this oxide compound, behind 3 hours mixings, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 1
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 2
Take by weighing Y 2O 3Powder 80 grams, Gd 2O 3Powder 874 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 149 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.122Gd 0.833Eu 0.045) BO 3Fluorescent material.
Embodiment 3
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid mixture of these three kinds of powder being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, through 800 ℃ of pre-burnings 4 hours, 1400 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 4
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 10% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 426 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 5
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 20% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 378 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 6
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 50% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 236 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 7
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 80% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 95 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 8
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 276 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 9
Take by weighing Y 2O 3Powder 276 grams, Gd 2O 3Powder 666 grams, Eu 2O 3Powder 46 grams, Sm 2O 3Powder 12 grams.With the 8N concentrated hydrochloric acid this four kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.379Gd 0.569Eu 0.04Sm 0.012) BO 3Fluorescent material.
Embodiment 10
Take by weighing Y 2O 3Powder 279.5 grams, Gd 2O 3Powder 670 grams, Eu 2O 3Powder 45.5 grams, BaCl 2Powder 13.5 grams.With the 8N concentrated hydrochloric acid this four kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.3802Gd 0.5702Eu 0.0396Ba 0.01) BO 3Fluorescent material.
Embodiment 11
Take by weighing Y 2O 3Powder 290 grams, Gd 2O 3Powder 698 grams, Eu 2O 3Powder 12 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.396Gd 0.594Eu 0.01) BO 3Fluorescent material.
Embodiment 12
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 670 grams, Eu 2O 3Powder 50 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.572Eu 0.044) BO 3Fluorescent material.
Embodiment 13
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, burnt till in 6 hours through 900 ℃.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 14
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, 1100 ℃ were burnt till in 6 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 15
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these three kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, 1500 ℃ were burnt till in 6 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 16
Take by weighing Y 2O 3Powder 954 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these two kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 223 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Y 0.97Eu 0.03) BO 3Fluorescent material.
Embodiment 17
Take by weighing Gd 2O 3Powder 954 grams, Eu 2O 3Powder 46 restrains, and after with the 8N concentrated hydrochloric acid these two kinds of powdered mixture being dissolved, adds oxalic acid solution and makes the generation oxalate coprecipitation, and the hot water wash of using 70-100 ℃ is to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 142 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain structural formula is (Gd 0.953Eu 0.047) BO 3Fluorescent material.
Embodiment 18
Take by weighing Y 2O 3Powder 433.5 grams, Gd 2O 3Powder 517.5 grams, Eu 2O 3Powder 49 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 179 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.55Gd 0.41Eu 0.04) BO 3Fluorescent material.
Embodiment 19
Take by weighing Y 2O 3Powder 394 grams, Gd 2O 3Powder 557 grams, Eu 2O 3Powder 49 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 175 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.51Gd 0.45Eu 0.04) BO 3Fluorescent material.
Embodiment 20
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 25% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 355 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 21
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 45% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 260 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 22
Take by weighing Y 2O 3Powder 173 grams, Gd 2O 3Powder 611 grams, Eu 2O 3Powder 216 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 157 gram boric acid, 3 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.25Gd 0.55Eu 0.2) BO 3Fluorescent material.
Embodiment 23
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, 1000 ℃ were burnt till in 6 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 24
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 3 hours mixed evenly after, 1200 ℃ were burnt till in 6 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 25
Take by weighing Y 2O 3Powder 280 grams, Gu 2O 3Powder 674 grams, Eu 2O 3Powder 46 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 10 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
Embodiment 26
Take by weighing Y 2O 3Powder 280 grams, Gd 2O 3Powder 674 grams, Eu 2O 3Powder 46 grams.With the 8N concentrated hydrochloric acid this three kinds of powdered mixture dissolving after, add oxalic acid solution and make the generation oxalate coprecipitation, with 70-100 ℃ hot water wash to pH=6-7.Obtain the oxalate precipitation of water content 35% after the solid-liquid separation.In 1 kilogram of this oxalate precipitation, add 166 gram boric acid, 20 hours mixed evenly after, through 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings were burnt till in 4 hours.The sample that burns till after adding entry and pellet shot from a slingshot Ball milling, the 500 orders after scouring that sieves, oven dry then, 200 order nylon wires sieve and obtain (Y 0.384Gd 0.576Eu 0.04) BO 3Fluorescent material.
According to the method for embodiment 1, only change the fluorescent material that following condition prepares embodiment 27-32.
Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 Embodiment 32
This burning of mixing time calcined temperature temperature Press embodiment 1 in 1 hour and press embodiment 1 2 hours with embodiment 1 with embodiment 1 With 1 700 ℃ 1100 ℃ of embodiment With 1 950 ℃ 1100 ℃ of embodiment With 1 900 ℃ 1000 ℃ of embodiment With 1 900 ℃ 1500 ℃ of embodiment
According to the method for embodiment 1, only change the fluorescent material that following condition prepares embodiment 33-37.
Embodiment 33 4 hours pre-burning time, 5 hours this burning time
Embodiment 34 4 hours pre-burning time, 6 hours this burning time
Embodiment 35 3 hours pre-burning time, 4 hours this burning time
Embodiment 36 3 hours pre-burning time, 5 hours this burning time
Embodiment 37 3 hours pre-burning time, 6 hours this burning time
According to the method for embodiment 13, change the fluorescent material that following condition prepares embodiment 38-45.
Embodiment 38 Calcination time is 4 hours
Embodiment 39 Calcination time is 8 hours
Embodiment 40 Calcination time is 10 hours
Embodiment 41 The dosage of boric acid becomes 276 grams
Embodiment 42 Mixing time is 1 hour
Embodiment 43 Mixing time is 2 hours
Embodiment 44 Mixing time is 10 hours
Embodiment 45 Mixing time is 20 hours
Method according to embodiment 9 changes the fluorescent material that following condition prepares embodiment 46-61
?Y 2O 3Dosage (g) ??Gd 2O 3Dosage (g) ?Eu 2O 3Dosage (g) Sm 2O 3Dosage (g) ??Dy 2O 3Dosage (g) The oxalate water content Boric acid dosage (g) Structural formula
Embodiment 46 ????277 ????665.4 ????45.6 - ????12 ?35％ 166 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 47 ????277 ????665.4 ????45.6 - ????12 ?10％ 425 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 48 ????277 ????665.4 ????45.6 - ????12 ?20％ 378 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 49 ????277 ????665.4 ????45.6 - ????12 ?25％ 355 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 50 ????277 ????665.4 ????45.6 - ????12 ?45％ 260 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 51 ????277 ????665.4 ????45.6 - ????12 ?50％ 240 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 52 ????277 ????665.4 ????45.6 - ????12 ?80％ 95 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 53 ????277 ????665.4 ????45.6 - ????12 ?35％ 267 (Y 0.38Gd 0.57Eu 0.04Dy 0.01)BO 3
Embodiment 54 ???277.5 ????666 ????45.5 ????6 ????6 ?35％ 166 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 55 ???277.5 ????666 ????45.5 ????6 ????6 ?10％ 425 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 56 ???277.5 ????666 ????45.5 ????6 ????6 ?20％ 378 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 57 ???277.5 ????666 ????45.5 ????6 ????6 ?25％ 355 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 58 ???277.5 ????666 ????45.5 ????6 ????6 ?45％ 260 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 59 ???277.5 ????666 ????45.5 ????6 ????6 ?50％ 240 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 60 ???277.5 ????666 ????45.5 ????6 ????6 ?80％ 95 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
Embodiment 61 ???277.5 ????666 ????45.5 ????6 ????6 ?35％ 267 (Y 0.38Gd 0.57Eu 0.04Sm 0.005Dy 0.005)BO 3
According to the method for embodiment 46, only change the fluorescent material that following calcination mode prepares embodiment 62-68
The calcination mode
Embodiment 62 1100 ℃ of 6 hours once-firings
Embodiment 63 1100 ℃ of 4 hours once-firings
Embodiment 64 1100 ℃ of 8 hours once-firings
Embodiment 65 900 ℃ of pre-burnings 4 hours, 1200 ℃ of these burnings 4 hours
Embodiment 66 900 ℃ of pre-burnings 4 hours, 1500 ℃ of these burnings 4 hours
Embodiment 67 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings 5 hours
Embodiment 68 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings 5 hours
Only change the fluorescent material that following calcination mode prepares embodiment 69-75 according to embodiment 54 methods
The calcination mode
Embodiment 69 1100 ℃ of 6 hours once-firings
Embodiment 70 1100 ℃ of 4 hours once-firings
Embodiment 71 1100 ℃ of 8 hours once-firings
Embodiment 72 900 ℃ of pre-burnings 4 hours, 1200 ℃ of these burnings 4 hours
Embodiment 73 900 ℃ of pre-burnings 4 hours, 1500 ℃ of these burnings 4 hours
Embodiment 74 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings 5 hours
Embodiment 75 900 ℃ of pre-burnings 4 hours, 1100 ℃ of these burnings 5 hours
According to the method for embodiment 1, only change the fluorescent material that following condition prepares embodiment 76-81
Embodiment Y 2O 3Dosage (g) Gd 2O 3Dosage (g) Eu 2O 3Dosage (g) The calcination mode Structural formula
Embodiment 76 embodiment 77 embodiment 78 embodiment 79 embodiment 80 embodiment 81 ????954 ????954 ????954 ????- ????292 ????80 ????- ????- ????- ????954 ????698 ????874 ????46 ????46 ????46 ????46 ????12 ????46 1100 ℃ 6 hours 1500 ℃ 8 hours 1000 ℃ 4 hours 1100 ℃ 6 hours 1100 ℃ 6 hours 1100 ℃ 6 hours (Y 0.97Eu 0.03)BO 3(Y 0.97Eu 0.03)BO 3(Y 0.97Eu 0.03)BO 3(Gd 0.953Eu 0.047)BO 3(Y 0.396Gd 0.594Eu 0.01)BO 3(Y 0.122Gd 0.833Eu 0.045)BO 3
According to the method for embodiment 13, only change the fluorescent material that following condition prepares embodiment 82-85
Embodiment 82 embodiment 83 embodiment 84 embodiment 85 Oxalate water content 10% 20% 50% 80% Boric acid dosage (g) 425 grams 378 grams 236 grams 95 grams
The sample testing of embodiment 1-85 and comparative example 1-2 be the results are shown in table 1, utilize the fluorescent material of the inventive method preparation to have high brightness as can be seen from the data of table 1, purity of color is better, the characteristics of particle good dispersity.
Table 1
Brightness (Br%) 147nm Chromaticity coordinates x Chromaticity coordinates y ????D 50????(μm) ????Dc
Comparative example 1 ????94％ 0.6487 ?0.3510 ????3.45 ????0.45
Comparative example 2 ????98％ 0.6423 ?0.3574 ????3.10 ????0.42
Embodiment 1 ????115％ 0.6487 ?0.3512 ????2.96 ????0.35
Embodiment 2 ????108％ 0.6438 ?0.3550 ????2.96 ????0.34
Embodiment 3 ????103％ 0.6447 ?0.3540 ????3.00 ????0.37
Embodiment 4 ????102％ 0.6434 ?0.3565 ????2.95 ????0.37
Embodiment 5 ????108％ 0.6451 ?0.3544 ????2.98 ????0.34
Embodiment 6 ????110％ 0.6447 ?0.3550 ????2.96 ????0.35
Embodiment 7 ????107％ 0.6426 ?0.3572 ????2.95 ????0.38
Embodiment 8 ????114％ 0.6441 ?0.3558 ????2.94 ????0.36
Embodiment 9 ????119％ 0.6494 ?0.3504 ????3.04 ????0.35
Embodiment 10 ????119％ 0.6477 ?0.3521 ????2.99 ????0.34
Embodiment 11 ????108％ 0.6415 ?0.3574 ????2.93 ????0.32
Embodiment 12 ????117％ 0.6485 ?0.3514 ????3.00 ????0.35
Embodiment 13 ????105％ 0.6447 ?0.3550 ????2.98 ????0.36
Embodiment 14 ????120％ 0.6494 ?0.3500 ????3.08 ????0.33
Embodiment 15 ????102％ 0.6456 ?0.3538 ????3.05 ????0.35
Embodiment 16 ????92％ 0.6454 ?0.3541 ????3.05 ????0.35
Embodiment 17 ????92％ 0.6454 ?0.3541 ????3.05 ????0.35
Embodiment 18 ????101％ 0.6457 ?0.3528 ????2.98 ????0.35
Embodiment 19 ????102％ 0.6457 ?0.3529 ????3.00 ????0.37
Embodiment 20 ????109％ 0.6474 ?0.3524 ????3.02 ????0.35
Embodiment 21 ????112％ 0.6471 ?0.3521 ????3.00 ????0.37
Embodiment 22 ????103％ 0.6501 ?0.3478 ????3.01 ????0.34
Embodiment 23 ????110％ 0.6472 ?0.3521 ????2.94 ????0.33
Embodiment 24 ????114％ 0.6471 ?0.3525 ????3.00 ????0.35
Embodiment 25 ????115％ 0.6471 ?0.3521 ????3.00 ????0.35
Embodiment 26 ????116％ 0.6472 ?0.3520 ????3.05 ????0.33
Embodiment 27 ????110％ 0.6471 ?0.3523 ????3.02 ????0.35
Embodiment 28 ????114％ 0.6469 ?0.3526 ????2.96 ????0.35
Embodiment 29 ????98％ 0.6443 ?0.3538 ????2.98 ????0.36
Embodiment 30 ????113％ 0.6470 ?0.3525 ????3.01 ????0.34
Embodiment 31 ????113％ 0.6470 ?0.3528 ????3.04 ????0.36
Embodiment 32 ????99％ 0.6468 ?0.3525 ????3.03 ????0.37
Embodiment 33 ????115％ 0.6470 ?0.3525 ????2.97 ????0.35
Embodiment 34 ????113％ 0.6472 ?0.3525 ????3.00 ????0.34
Embodiment 35 ????108％ 0.6469 ?0.3528 ????2.96 ????0.35
Embodiment 36 ????110％ 0.6470 ?0.3527 ????3.02 ????0.35
Embodiment 37 ????107％ 0.6470 ?0.3528 ????3.00 ????0.35
Embodiment 38 ????105％ 0.6460 ?0.3533 ????2.98 ????0.37
Embodiment 39 ????103％ 0.6461 ?0.3534 ????2.99 ????0.36
Embodiment 40 ????97％ 0.6460 ?0.3535 ????3.02 ????0.37
Embodiment 41 ????118％ 0.6473 ?0.3521 ????2.96 ????0.34
Embodiment 42 ????111％ 0.6470 ?0.3525 ????2.96 ????0.34
Embodiment 43 ????113％ 0.6471 ?0.3527 ????2.98 ????0.34
Embodiment 44 ????114％ 0.6472 ?0.3527 ????3.00 ????0.34
Embodiment 45 ????114％ 0.6472 ?0.3526 ????3.01 ????0.34
Embodiment 46 ????118％ 0.6773 ?0.3524 ????3.01 ????0.35
Embodiment 47 ????105％ 0.6470 ?0.3524 ????3.00 ????0.35
Embodiment 48 ????105％ 0.6471 ?0.3526 ????3.02 ????0.35
Embodiment 49 ????112％ 0.6470 ?0.3524 ????3.00 ????0.35
Embodiment 50 ????113％ 0.6468 ?0.3530 ????2.99 ????0.36
Embodiment 51 ????107％ 0.6469 ?0.3527 ????3.01 ????0.34
Embodiment 52 ????106％ 0.6468 ?0.3527 ????2.96 ????0.36
Embodiment 53 ????119％ 0.6472 ?0.3524 ????3.00 ????0.34
Embodiment 54 ????119％ 0.6474 ?0.3523 ????3.00 ????0.34
Embodiment 55 ????104％ 0.6469 ?0.3528 ????3.02 ????0.35
Embodiment 56 ????106％ 0.6470 ?0.3524 ????3.02 ????0.35
Embodiment 57 ????109％ 0.6470 ?0.3524 ????3.02 ????0.35
Embodiment 58 ????112％ 0.6472 ?0.3524 ????3.00 ????0.36
Embodiment 59 ????108％ 0.6471 ?0.3525 ????2.98 ????0.37
Embodiment 60 ????105％ 0.6472 ?0.3523 ????2.98 ????0.37
Embodiment 61 ????120％ 0.6472 ?0.3524 ????3.02 ????0.35
Embodiment 62 ????122％ 0.6471 ?0.3525 ????3.00 ????0.35
Embodiment 63 ????114％ 0.6468 ?0.3528 ????3.01 ????0.36
Embodiment 64 ????108％ 0.6469 ?0.3524 ????3.00 ????0.36
Embodiment 65 ????119％ 0.6470 ?0.3525 ????3.00 ????0.35
Embodiment 66 ????108％ 0.6465 ?0.3530 ????3.02 ????0.36
Embodiment 67 ????119％ 0.6470 ?0.3524 ????3.03 ????0.36
Embodiment 68 ????116％ 0.6470 ?0.3526 ????3.00 ????0.35
Embodiment 69 ????121％ 0.6470 ?0.3526 ????2.98 ????0.35
Embodiment 70 ????113％ 0.6472 ?0.3524 ????2.99 ????0.37
Embodiment 71 ????106％ 0.6468 ?0.3527 ????2.98 ????0.36
Embodiment 72 ????120％ 0.6470 ?0.3525 ????3.00 ????0.35
Embodiment 73 ????110％ 0.6471 ?0.3526 ????3.01 ????0.35
Embodiment 74 ????118％ 0.6470 ?0.3527 ????3.03 ????0.36
Embodiment 75 ????114％ 0.6471 ?0.3526 ????2.96 ????0.37
Embodiment 76 ????94％ 0.6470 ?0.3524 ????2.98 ????0.36
Embodiment 77 ????93％ 0.6469 ?0.3524 ????3.00 ????0.35
Embodiment 78 ????92％ 0.6471 ?0.3527 ????3.00 ????0.35
Embodiment 79 ????94％ 0.6471 ?0.3527 ????3.00 ????0.34
Embodiment 80 ????100％ 0.6460 ?0.3531 ????3.02 ????0.35
Embodiment 81 ????102％ 0.6471 ?0.3527 ????3.02 ????0.35
Embodiment 82 ????110％ 0.6472 ?0.3525 ????3.00 ????0.37
Embodiment 83 ????113％ 0.6472 ?0.3524 ????3.01 ????0.35
Embodiment 84 ????116％ 0.6471 ?0.3524 ????2.98 ????0.34
Embodiment 85 ????109％ 0.6471 ?0.3524 ????2.97 ????0.34

Claims (23)

1. a structural formula is (Y AGd BEu C) BO 3The preparation method of red fluorescence powder, it is characterized in that it may further comprise the steps:
(a) mol ratio according to each material in the structural formula of following rare-earth oxalate takes by weighing yttrium oxide, europium sesquioxide; Or europium sesquioxide, gadolinium sesquioxide; Or yttrium oxide, europium sesquioxide, gadolinium sesquioxide; Make it be dissolved in an amount of concentrated hydrochloric acid or nitric acid, be made into the clear rare earth feed liquid, add oxalic acid and stirring by stoichiometry, making oxalate co-precipitation obtain structural formula is [(Y AGd BEu C) 2(C 2O 4) 3] rare-earth oxalate precipitation, the numerical value of A is 0-0.99 in the formula, the numerical value of B is 0-0.99, the numerical value of C is 0.01-0.20, and must satisfy 0＜A+B≤0.99;
(b) with the above-mentioned rare-earth oxalate precipitation of hot wash, filter, solid-liquid separation, and sneak into excessive boric acid;
(c) in 700 ℃-1500 ℃ air atmosphere, after calcination 2-10 hour, obtain the yttrium borate europium, or boric acid europium gadolinium, or yttrium borate europium gadolinium fluorescent material;
(d) Ball milling, 500 orders sieve washing, the oven dry;
(e) on 200 order nylon wires, sieve again and can obtain product.
2. the preparation method of red fluorescence powder as claimed in claim 1, its feature also are in step (b) it is until PH=6-7 with 70-100 ℃ hot wash oxalate precipitation.
3. the preparation method of red fluorescence powder as claimed in claim 1, its feature also is described boric acid and rare-earth oxalate middle-weight rare earths ionic mol ratio 〉=1.
4. the preparation method of red fluorescence powder as claimed in claim 1, its feature is that also described boric acid is the form batch mixing with solid boric acid, mixing time is 1-20 hour.
5. the preparation method of red fluorescence powder as claimed in claim 1, its feature are that also described rare-earth oxalate precipitation also comprises the moisture content of 10-80% weight.
6. the preparation method of red fluorescence powder as claimed in claim 5, its feature are that also described rare-earth oxalate precipitation comprises the moisture content of 20-50% weight preferably.
7. the preparation method of red fluorescence powder as claimed in claim 6, its feature are that also described rare-earth oxalate precipitation better comprises the moisture content of 25-45% weight.
8. the preparation method of red fluorescence powder as claimed in claim 7, its feature are that also the calcination temperature of described rare-earth oxalate precipitation and mebor is preferably 1000-1200 ℃.
9. the preparation method of red fluorescence powder as claimed in claim 1, its feature are that also the calcination mode of described rare-earth oxalate precipitation and mebor is a calcination.
10. the preparation method of red fluorescence powder as claimed in claim 1, its feature are that also the calcination mode of described rare-earth oxalate precipitation and mebor can also be first 700-950 ℃ of pre-burning, again in 1000-1500 ℃ this burning.
11. as the preparation method of each described red fluorescence powder of claim 1-10, its feature also is described oxalate structural formula [(Y AGd BEu C) 2(C 2O 4) 3] in the numerical value of A be preferably 0.15-0.55, the numerical value of B is preferably 0.45-0.85, the numerical value of C is preferably 0.01-0.05.
12. a structural formula is (Y AGd BEu CMe W) BO 3The preparation method of red fluorescence powder, it is characterized in that it may further comprise the steps:
(a) mol ratio according to each material in the structural formula of following rare-earth oxalate takes by weighing yttrium oxide, europium sesquioxide; Or europium sesquioxide, gadolinium sesquioxide; Or yttrium oxide, europium sesquioxide, gadolinium sesquioxide; Make it be dissolved in an amount of concentrated hydrochloric acid or nitric acid, be made into the clear rare earth feed liquid, and splash into therein and contain Nd 3+, Sm 3+, Dy 3+, Ca 2+Or Ba 2+In a kind of or several impurities ion solution, add oxalic acid and stir by stoichiometry, making oxalate co-precipitation obtain structural formula is [(Y AGd BEu CMe W) 2(C 2O 4) 3] rare-earth oxalate precipitation, the numerical value of A is 0-0.99 in the formula, the numerical value of B is 0-0.99, the numerical value of C is 0.01-0.20, and must satisfy 0＜A+B≤0.99;
When Me represents Nd 3+, Sm 3+Or Dy 3+The time
W equals 0.001% (2A+2B+2C) to 0.5% (2A+2B+2C),
When Me represents Ca 2+Or Ba 2+The time
W equals 0.5% (2A+2B+2C) to 2% (2A+2B+2C);
(b) with the above-mentioned rare-earth oxalate precipitation of hot wash, filter, solid-liquid separation, and sneak into excessive boric acid;
(c) in 700 ℃-1500 ℃ air atmosphere, after calcination 2-10 hour, obtain the yttrium borate europium, or boric acid europium gadolinium, or yttrium borate europium gadolinium fluorescent material;
(d) Ball milling, 500 orders sieve washing, the oven dry;
(e) on 200 order nylon wires, sieve again and can obtain product.
13. the preparation method of red fluorescence powder as claimed in claim 12, its feature also are the Nd that contains described in the steps A 3+, Sm 3+, Dy 3+, Ca 2+Or Ba 2+In a kind of or several impurities ion solution be to contain impurity element Nd, Sm, Dy, the solution of the soluble compound of Ca or Ba, or with described impurity element Nd, Sm, Dy, the acid solution that the oxide compound of Ca or Ba is made into earlier.
14. the preparation method of red fluorescence powder as claimed in claim 12, its feature also are in step (b) it is until PH=6-7 with 70-100 ℃ hot wash oxalate.
15. the preparation method of red fluorescence powder as claimed in claim 12, its feature also are described boric acid and rare-earth oxalate middle-weight rare earths ionic mol ratio 〉=1.
16. the preparation method of red fluorescence powder as claimed in claim 12, its feature are that also described boric acid is the form batch mixing with solid boric acid, mixing time is 1-20 hour.
17. the preparation method of red fluorescence powder as claimed in claim 12, its feature are that also described oxalate also comprises the moisture content of 10-80% weight.
18. the preparation method of red fluorescence powder as claimed in claim 17, its feature are that also described rare-earth oxalate comprises the moisture content of 20-50% weight preferably.
19. the preparation method of red fluorescence powder as claimed in claim 18, its feature are that also described rare-earth oxalate better comprises the moisture content of 25-45% weight.
20. the preparation method of red fluorescence powder as claimed in claim 12, its feature are that also the calcination temperature of described oxalate and mebor is preferably 1000-1500 ℃.
21. the preparation method of red fluorescence powder as claimed in claim 12, its feature are that also the calcination mode of described rare-earth oxalate and mebor is a calcination.
22. the preparation method of red fluorescence powder as claimed in claim 12, its feature are that also the calcination mode of described rare-earth oxalate and mebor can also be earlier 700-950 ℃ of pre-burning, again in 1000-1500 ℃ this burning.
23. as the preparation method of each described red fluorescence powder of claim 12-22, its feature also is described oxalate structural formula [(Y AGd BEu CMe W) 2(C 2O 4) 3] in the numerical value of A be preferably 0.15-0.55, the numerical value of B is preferably 0.45-0.85, the numerical value of C is preferably 0.01-0.05.
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