CN101967375A - Method for preparing red barium magnesium germanate luminous material - Google Patents
Method for preparing red barium magnesium germanate luminous material Download PDFInfo
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- CN101967375A CN101967375A CN200910157357XA CN200910157357A CN101967375A CN 101967375 A CN101967375 A CN 101967375A CN 200910157357X A CN200910157357X A CN 200910157357XA CN 200910157357 A CN200910157357 A CN 200910157357A CN 101967375 A CN101967375 A CN 101967375A
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Abstract
The invention belongs to the field of rare earth luminous materials and particularly relates to a method for preparing a red barium magnesium germanate luminous material. The method comprises the following specific steps of: grinding analytically pure reaction raw materials, namely barium salt, magnesium salt, Ge2O7, an activator and corresponding fused salt according to a stoichiometric ratio; performing fused salt reaction on the ground raw materials in a crucible at the temperature of between 850 and 1,200 DEG C for 6 to 10 hours to obtain a solid molten product; and washing the solid molten product by deionized water and drying to obtain the required product. The method is easy to implement and enables repeated operation.
Description
Technical field
The invention belongs to rare earth luminescent material field, be specifically related to a kind of preparation method of red magnesium barium germinate luminescent material.
Background technology
In the past few decades, phosphor is answered as showing fields such as being used for flat pannel display, Field Emission Display, plasma display, thin-film electroluminescence (TFEL) material with luminescent material and is paid close attention to widely.A large amount of work of past all is that commercial fluorescent material is carried out modification etc. to improve its luminous correlation technique index.As to Y
2O
3: Eu
3+, YAG:Eu
3+The preparation method of twinkler, the research of technology modification and coating very many [1-9].To the research shortcoming research extensively and profoundly of novel light-emitting body, following progress along with information display technology, more and more higher to the qualitative performance requirements of luminescent powder, so the needs of development of new luminescent material are handed over more urgent.Phosphor mainly is made up of matrix and active ions, and selecting suitable matrix and activator is the basis of design synthesizing inorganic twinkler.Inorganic body kind as matrix has a lot, and the matrix system that wherein is widely studied has tungstate, molybdate, silicate, borate, phosphoric acid salt, vanadate, oxide compound, oxyhalogenide, sulfide and oxysulfide etc.; Mainly contain EU as active ions
3+, Tb
3+, Du
3+, Sm
3+Deng lanthanide ion and some transition metal ions such as Mn
2+, Cr
3+, V
3+Deng.Germanate is as a kind of novel substrate material, and is less to its research.The germanate luminescent material of having reported has YinGe
2O
7: Tb
3+[10], LaAlGe
2O
7: Pr
3+[11,12], Gd
2GeO
5: Eu
3+, Tb
3+, Bi
3+[13], Sr
2La
8(GeO
4) O
2: Eu
3+[14] etc., Ba
2MgGe
2O
7: Eu
3+Yet there are no report, Ba as a kind of novel red luminescent material
2MgGe
2O
7Stable as the luminous host physicochemical property, can be directly synthetic by the method for consolidating, also can under relatively low temperature, obtain by molten-salt growth method.Fused salt answers medium to punish the long liquid environment that relevant temperature is provided severely without mercy for crystal as a kind of effectively opening up.Molten-salt growth method is a kind of simple, applicable to multiple field and low-cost method, can control synthetic to crystal morphology by changing parameters such as fused salt kind and temperature of reaction.Therefore, obtain Ba by molten-salt growth method
2MgGe
2O
7: Eu
3+Novel material has very big researching value and exploitation meaning.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of novel red magnesium barium germinate fluorescent powder for displaying.
The preparation method of the novel red magnesium barium germinate fluorescent powder for displaying that the present invention proposes is for adopting molten-salt growth method synthesizing micron-grade magnesium barium germinate (Ba
2MgGe
2O
7: Eu
3+) high brightness emitting red light body.This Eu
3+The activated twinkler can produce Eu under the 393nm ultraviolet excitation
3+613nm feature emission peak.
The preparation method of the novel red magnesium barium germinate fluorescent powder for displaying that the present invention proposes, the gained magnesium barium germinate fluorescent powder consist of Ba
2MgGe
2O
7: Eu
3+, 0＜x＜1, concrete steps are as follows:
Take by weighing analytically pure reaction raw materials barium salt, magnesium salts, GeO2 (A.R.), activator and corresponding fused salt in agate mortar by stoichiometric ratio, grind, make reaction raw materials evenly and reach certain fineness, ground raw material is packed into the fused salt reaction takes place in the corundum crucible, temperature of reaction is 650～1200 ℃, reaction times is 3～10 hours, obtain the solid product that melts together, through the washing of deionized water, flush away fused salt, drying promptly gets required product.
Among the present invention, the value of described X is 0.02～0.50.
Among the present invention, described barium salt can in barium carbonate, barium oxalate, barium oxide, barium acetate or the hydrated barta etc. any.
Institute among the present invention, described magnesium salts can in magnesium basic carbonate, magnesium oxalate, magnesium oxide, magnesium acetate or the magnesium hydroxide etc. any.
Among the present invention, described activator can in europium sesquioxide, europium carbonate, acetate europium, europium hydroxide or the oxalic acid europium etc. any.
Among the present invention, described fused salt can be NaCl, KCI, LiCI, LiNO
3Or NaNO
3In any, perhaps be the mixing salt that NaCI and KCI form.
Among the present invention, described NaCI and KCI mix molar ratio be in 1: 1,1: 2 or 1: 3 any.
Among the present invention, 60～100 ℃ deionized water wash is adopted in the washing of described deionized water.Washing times is generally 3-6 time.
Among the present invention, be 20-28 hour described time of drying, and drying temperature is 75-90 ℃.
The present invention adopts the fused salt reaction, can obtain required fluorescent material at lower roasting temperature, and the particle diameter of gained fluorescent material is very little, and its pattern can pass through the different fused salt kind of regulation and control and difference.The inventive method is simple, and favorable reproducibility is applicable to batch process.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
By stoichiometric ratio Ba
2MgGe
2O
7: Eu
3+ 0.08Take by weighing 0.397 gram BaCO
3, 0.097 gram (MgCO
3)
4Mg (OH)
25H
2O, 0.209 gram GeO
2, 0.014 gram Eu
2O
3With 0.6136 gram NaCI and 0.7828 gram KCI, putting into agate mortar is ground to reaction raw materials and mixes and reach certain fineness (being generally about 30 minutes), change over to then in the corundum crucible in 850 ℃ of roastings after 6 hours furnace cooling take out to room temperature, soak with about 60 ℃ deionized waters, and repeatedly washing, use AgNO
3The no CI of solution check
-Till, 80 ℃ of dry 24h in baking oven promptly get～Ba of 2um
1:92MgGe
2O
7: Eu
3+ 0.08Powder.
Embodiment 2
By stoichiometric ratio Ba
1:92MgGe
2O
7: Eu
3+ 0.08Take by weighing 0.294 gram BaCO
3, 0.097 gram (MgCO
3)
4Mg (OH)
25H
2O, 0.209 gram GeO
2, 0.019 gram Eu
2(CO
3)
3With 0.580 gram NaCI (0.010mol), putting into agate mortar is ground to reaction raw materials and mixes and reach certain fineness (being generally about 30 minutes), change over to then in the corundum crucible in 750 ℃ of roastings after 3 hours furnace cooling take out to room temperature, soak with about 70 ℃ deionized waters, and repeatedly washing, use AgNO
3The no CI of solution check
-Till, 80 ℃ of dry 24h in baking oven promptly get～Ba of 2um
1:92MgGe
2O
7: Eu
3+ 0.08Powder.
Embodiment 3
By stoichiometric ratio Ba
1:92MgGe
2O
7: Eu
3+ 0.08Take by weighing 0.379 gram BaCO
3, 0.097 gram (MgCO
3)
4Mg (OH)
25H
2O, 0.209 gram GeO2,0.014 gram Eu
2O
3Restrain with reaction raw materials quality triple NaCI2.097, putting into agate mortar is ground to reaction raw materials and mixes and reach certain fineness (being generally about 30 minutes), change over to then in the corundum crucible in 900 ℃ of roastings after 8 hours furnace cooling take out to room temperature, soak with about 100 ℃ deionized waters, and repeatedly washing, use AgNO
3The no CI of solution check
-Till, 85 ℃ of dry 24h promptly get～2umBa in baking oven
1:92MgGe
2O
7: Eu
3+ 0.04Powder.
Embodiment 4
By stoichiometric ratio Ba
1:92MgGe
2O
7: Eu
3+ 0.08Take by weighing 0.379 gram BaCO
3, 0.097 gram (MgCO
3)
4Mg (OH)
25H
2O, 0.209 gram GeO
2, 0.014 gram Eu
2O
3Add the KCI of reactant quality 100% more therein as fused salt, putting into agate mortar is ground to reaction raw materials and mixes and reach certain fineness (being generally about 30 minutes), change over to then in the corundum crucible in 850 ℃ of roastings after 6 hours furnace cooling take out to room temperature, with the block powder deionized water dissolving of gained, ageing 12 hours is with the water elimination.Use deionized water dissolving again.
Ageing is filtered, and repeated multiple times is removed unnecessary KCI salt washing, till the no Cl-of AgNO3 solution check.The white powder that filtration is obtained behind 80 ℃ of oven drying 24h, promptly get the synthetic of wanting 2 μ m powders.
Embodiment 5
By stoichiometric ratio Ba
1.92MgGe
2O
7: Eu
3+ 0.08Take by weighing 0.379 gram BaCO
3, 0.097 gram (MgCO
3)
4Mg (OH)
25H
2O, 0.209 gram GeO
2, 0.014 gram Eu
2O
3The NaCI that adds 2 times of reaction raw materials total masses more therein is as fused salt, putting into agate mortar is ground to reaction raw materials and mixes and reach certain fineness (being generally about 30 minutes), change in the corundum crucible then and cover earthenware and cover, after 6 hours, taking-up that furnace cooling has arrived room temperature is with the block powder deionized water dissolving of gained in 850 ℃ of roastings, left standstill 12 hours, with the water elimination.Use deionized water dissolving again, leave standstill, filter repeated multiple times, unnecessary KCI salt washing is removed, till the no Cl-of AgNO3 solution check.The white powder that filtration is obtained behind 80 ℃ of oven drying 24h, promptly get the synthetic of wanting 2 μ m powders.
Embodiment 6
By stoichiometric ratio Ba
1.92MgGe
2O
7: Eu
3+ 0.04Take by weighing 0.300 gram BaO, 0.040 gram MgO), 0.209 gram GeO
2, 0.007 gram Eu
2O
3, more therein roller go into reactant total mass 100% KCI as fused salt, put into agate mortar and grind certain hour (being generally about 30 minutes), raw material KCI salt washing is removed, use AgNO
3The no Cl of solution check
-Till.The white powder that filtration is obtained promptly gets the synthetic powder of wanting behind 80 ℃ of oven drying 24h.
Embodiment 7
By stoichiometric ratio Ba
1.92MgGe
2O
7: Eu
3+ 0.10Take by weighing 0.326 gram Ba, 0.058 gram Mg (OH)
2, 0.209 gram GeO
2, 0.024 gram Eu
2(CO
3)
3Roller is gone into the NaNO3 of reactant total mass 200% as fused salt therein again, putting into agate mortar ground about 30 minutes, make the raw material thorough mixing evenly and reach certain granularity, change over to then and cover crucible cover in the corundum crucible, in 800 ℃ of roastings after 6 hours, furnace cooling takes out to room temperature, the gained blocks of solid is soaked dissolving salt wherein with 90 ℃ of deionized waters, after leaving standstill 6 hours, furnace cooling takes out to room temperature, and the gained blocks of solid is soaked dissolving salt wherein with 90 ℃ of deionized waters, left standstill 6 hours, with the water elimination.Use the deionized water dissolving about 60 ℃ again, filter, repeated multiple times is removed unnecessary salt washing.The white powder that filtration is obtained promptly gets the synthetic powder of wanting behind 80 ℃ of oven drying 24h.
Embodiment 8
By stoichiometric ratio Ba
1.92MgGe
2O
7: Eu
3+ 0.06Take by weighing 0.437 gram BaC
2O
4, 0.040 gram MgO, 0.209 gram GeO
2, 0.017 gram Eu
2(C
2O
4)
3The NaCI that adds 10 times of reactant total masses more therein is as fused salt, putting into agate mortar ground about 30 minutes, make the raw material thorough mixing evenly and reach certain granularity, change in the corundum crucible then and cover the earthenware lid, in 1200 ℃ of roastings after 4 hours, furnace cooling takes out to room temperature, the gained blocks of solid is soaked dissolving salt wherein with 90 ℃ of deionized waters, left standstill 6 hours, the water elimination.Use the deionized water dissolving about 80 ℃ again, filter, repeated multiple times is removed the salt washing of unnecessary NaCl.Till the no Cl-of AgNO3 solution check.The white powder that filtration is obtained promptly gets the synthetic powder of wanting behind 80 ℃ of oven drying 24h.
Claims (5)
1. the preparation method of a red magnesium barium germinate luminescent material is characterized in that concrete steps are as follows: take by weighing analytically pure reaction raw materials barium salt, magnesium salts, Ge by stoichiometric ratio
2O
7, activator and corresponding fused salt grind, and ground raw material packed into the dissolved salt reaction takes place in the crucible, temperature of reaction is 850～1200 ℃, the reaction times is 6～10 hours, must melt thing admittedly, through the washing of deionized water, drying promptly gets required product.
2. the preparation method of red magnesium barium germinate luminescent material according to claim 1, the value that it is characterized in that described X is 0.25～0.80.
3. the preparation method of novel red magnesium barium germinate fluorescent powder for displaying according to claim 1 and 2, it is characterized in that described barium salt be in barium carbonate, barium oxalate, barium oxide, barium acetate or the hydrated barta any.
4. novel demonstration according to claim 1 and 2 is with the preparation method of red germanic acid magnesium fluorescent material, it is characterized in that described magnesium salts be in magnesium basic carbonate, magnesium oxalate, magnesium oxide, magnesium acetate or the magnesium hydroxide any.
5. the preparation method of novel red magnesium barium germinate fluorescent powder for displaying according to claim 1 and 2, it is characterized in that described activator be in europium sesquioxide, europium carbonate, acetate europium, europium hydroxide or the oxalic acid europium any.
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|---|---|---|---|
| CN200910157357XA CN101967375A (en) | 2009-07-28 | 2009-07-28 | Method for preparing red barium magnesium germanate luminous material |
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|---|---|---|---|
| CN200910157357XA CN101967375A (en) | 2009-07-28 | 2009-07-28 | Method for preparing red barium magnesium germanate luminous material |
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| CN101967375A true CN101967375A (en) | 2011-02-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774523A (en) * | 2018-07-06 | 2018-11-09 | 安徽腾奎智能科技有限公司 | A kind of red germanic acid magnesium barium fluorescent powder of novel display |
-
2009
- 2009-07-28 CN CN200910157357XA patent/CN101967375A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774523A (en) * | 2018-07-06 | 2018-11-09 | 安徽腾奎智能科技有限公司 | A kind of red germanic acid magnesium barium fluorescent powder of novel display |
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Application publication date: 20110209 |