CN1212366C - rareearth red fluorescent material, its preparation method and use - Google Patents

rareearth red fluorescent material, its preparation method and use Download PDF

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CN1212366C
CN1212366C CN 02136995 CN02136995A CN1212366C CN 1212366 C CN1212366 C CN 1212366C CN 02136995 CN02136995 CN 02136995 CN 02136995 A CN02136995 A CN 02136995A CN 1212366 C CN1212366 C CN 1212366C
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fluorescent material
water
rare
soluble
earth
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CN1483786A (en
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余锡宾
丁云峰
王则民
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Shanghai Normal University
University of Shanghai for Science and Technology
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Shanghai Normal University
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Abstract

The present invention discloses a red rare earth luminescent material which is expressed as the following chemical formula: (Eu<2(1-x)/3>M<x>MoO4)y. MC2O4, wherein the M is selected from magnesium, calcium, strontium and barium or combined alkali earth metal elements of the magnesium, the calcium, the strontium and the barium, x=0.001 to 0.1, and y=0.1 to 0.5. The present invention also discloses a preparation method of the red rare earth luminescent materials, which comprises the following steps: mixing oxalic acid or water-soluble oxalate, molybdic acid or water-soluble molybdate, water-soluble alkali earth metal salts and water-solubile europium salts as raw materials; grinding, washing and filtering the mixture and drying the filtered product. The photo-thermal stability of the red rare earth luminescent materials is high, the red rare earth luminescent materials can emit strong red fluorescence under the excitation of ultraviolet light, and the red rare earth luminescent materials with superfine granularity can be prepared. The reaction conditions of the preparation method are moderate, and the red rare earth luminescent materials can be prepared at room temperature. Thus, the energy consumption and the cost are greatly saved, and the luminescent materials with high purity are prepared.

Description

Rare-earth red fluorescent material, Preparation Method And The Use
Technical field
The present invention relates to rare-earth red fluorescent material, Preparation Method And The Use.
Background technology
Rare-earth red fluorescent material can be widely used in many fields, for example indicating meter, means of illumination, coating, optical transfer agricultural film, send the anti-counterfeiting mark of red fluorescence etc.In rare-earth luminescent material, use rare-earth europium as the fluorescence-activation source usually, the transition of positive trivalent europium ion produces red fluorescence.
It is (Y that Chinese invention patent ublic specification of application CN99124180.0 has disclosed a kind of structural formula AGd BEu c) BO 3Perhaps (Y AGd BEu cMe w) BO 3The preparation method of red fluorescence powder, this method comprises and prepares rare-earth oxalate [(Y with coprecipitation method earlier AGd BEu c) 2(C 2O 4) 3] or [(Y AGd BEu cMe w) 2(C 2O 4) 3], with the above-mentioned rare-earth oxalate precipitation of hot wash, filter solid-liquid separation then, and sneak into excessive boric acid, and in 700-1500 ℃ air atmosphere, after calcination 2-10 hour, obtain required fluorescent material, carry out Ball milling again, sieve, washing, steps such as oven dry obtain product.
Above-mentioned patent documentation is to make rare-earth red fluorescent material by high temperature sintering and ball milling, the main drawback of this high temperature sintering method is the energy consumption height, the cost height, thereby in high-temperature sintering process, introduce the impurity influence 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.
General rare-earth red fluorescent material makes with two kinds of methods basically at present, a kind of is exactly above-mentioned high-temperature sintering process, another kind method is to form title complex with rare earth ion and organic ligand, but the fluorescent material that this method makes exists photo and thermal stability relatively poor, is difficult to adapt to the shortcoming of actual service requirements.
Summary of the invention
An object of the present invention is to provide the rare-earth red fluorescent material that a kind of photo and thermal stability is good and luminous intensity is high, this material can make the fine rare earth red fluorescent powder of granularity.
Another object of the present invention provides a kind of preparation method of rare-earth red fluorescent material, this method can make the rare-earth red fluorescent material with above-mentioned premium properties with high purity, the mild condition of this method can at room temperature be reacted, and has saved energy and cost greatly.
A further object of the invention provides the purposes of rare-earth red fluorescent material.
Be achieved through the following technical solutions above-mentioned purpose of the present invention.
The invention provides a kind of rare-earth red fluorescent material, its composition is represented by following general formula:
(Eu 2(1-x)/3M xMoO 4) y·MC 2O 4
Wherein, M is the alkali earth metal that is selected from magnesium, calcium, strontium, barium or its combination, x=0.001-0.1, y=0.1-0.5.
It is calcium that above-mentioned rare-earth red fluorescent material is more preferably M, x=0.01-0.1, y=0.2-0.3.
The present invention also provides a kind of method for preparing rare-earth red fluorescent material, this method comprises: mix oxalic acid or water-soluble oxalate, molybdic acid or water-soluble molybdate, water-soluble alkali earth metal salt and water-soluble europium salt as raw material, at room temperature water grinds as dispersion agent, washing and filtering, oven dry obtains rare-earth red fluorescent material.
Above-mentioned preparation method also comprises the step that the gained rare-earth red fluorescent material is pulverized and sieved.
In above-mentioned preparation method, preferably, water-soluble oxalate is selected from potassium oxalate, ammonium oxalate and sodium oxalate, described water-soluble molybdate is selected from Sodium orthomolybdate, ammonium molybdate and potassium molybdate, described water-soluble alkali earth metal salt is selected from alkaline earth metal halide (being more preferably muriate), alkine earth metal nitrate and alkaline-earth metal acetate, and described water-soluble europium salt is selected from europium chloride and europium nitrate.
In above-mentioned preparation method, milling time is 0.5-2 hour.Bake out temperature is 60-200 ℃.
The present invention also provides the purposes of rare-earth red fluorescent material in following field: optical transfer agricultural film with light conversion agent, demonstration and illumination with fluorescent material, anti-fake fluorescent material and coating fluorescent material.
The photo and thermal stability of rare-earth red fluorescent material of the present invention is good, and the strong red fluorescence of emission can make the fine rare earth red fluorescent powder of granularity under ultraviolet excitation.The present invention prepares the reaction conditions gentleness of the method for described rare-earth red fluorescent material, at room temperature carried out, compare with high-temperature sintering process and to have saved energy and cost greatly, make highly purified fluorescent material, avoided introducing the problem of impurity effectively owing to high sintering temperature.In addition, the particle diameter of the fluorescent material that the inventive method makes is trickle, reaches micron to nano grade.Preparation method of the present invention compares with the method that prior art forms title complex, and it is much superior that the photo and thermal stability of obtained red fluorescence material is wanted.Rare-earth red fluorescent material of the present invention is of many uses, for example can be used as optical transfer agricultural film with light conversion agent, demonstration and illumination with fluorescent material, anti-fake fluorescent material and coating fluorescent material.
Description of drawings
Fig. 1 is the fluorescence spectrum figure of the rare-earth red fluorescent material of a better example of the present invention.
Embodiment
The invention provides a kind of rare-earth red fluorescent material, its composition is represented by following general formula:
(Eu 2(1-x)/3M xMoO 4) y·MC 2O 4
Wherein, M is the alkali earth metal that is selected from magnesium, calcium, strontium, barium or its combination, x=0.001-0.1, y=0.1-0.5.Preferably, M is a calcium, x=0.01-0.1, y=0.2-0.3.
This rare-earth red fluorescent material of the present invention is a double salt, and the form of double salt has higher photo and thermal stability than oxalate, so this fluorescent material has good luminous intensity and fluorescence lifetime.If supposing commercially available lamp is 100% with the luminous intensity of red light fluorescent powder (for example yttrium europium oxide ruddiness powder of Yaolong Non-ferrous Metal Co. Ltd., Shanghai's production), then the luminous intensity of red fluorescence material of the present invention can reach 95%, and price has only commercially available fluorescent material half.In addition, the luminous intensity of existing rare earth compounding fluorescent material (for example UTR ruddiness powder of company of Shanghai Normal University production) is about 85%.On the other hand, rare-earth red fluorescent material of the present invention after 2 months, is found that its fluorescence intensity is constant basically in outdoor placement.And after the fluorescent material of existing rare earth compounding form tested under the same conditions, its fluorescence intensity dropped to about 50% by initial 85%.
In rare-earth red fluorescent material of the present invention, the trivalent europium is as the fluorescence-activation source.And molybdate has a good sensibilized to the rare-earth europium ionic is luminous, can obviously improve the luminous intensity of rare earth ion.Also with above-mentioned standard metering luminous intensity, if supposing commercially available lamp is 100% with the luminous intensity of red light fluorescent powder (for example yttrium europium oxide ruddiness powder of Yaolong Non-ferrous Metal Co. Ltd., Shanghai's production), then the luminous intensity of red fluorescence material of the present invention can reach 95%, and the caoxalate europium double salt luminous intensity that does not contain molybdenum only has an appointment 40%.
The preparation method's of rare-earth red fluorescent material of the present invention principle is: select the raw material that chemical reaction can take place when grinding at low temperatures for use, these raw materials have good chemically reactive, form mixture fluor crystallite in process of lapping.By comparison, used raw material (as silicon-dioxide, aluminum oxide, lime carbonate, magnesiumcarbonate, europium sesquioxide etc.) does not react between mutually when low temperature in the conventional high temperature sintering technology, so can not form required fluor.So can only adopt high temperature sintering, its objective is the reaction that promotes between the raw material, form the mixture fluor.
The raw material of preparation rare-earth red fluorescent material of the present invention is oxalic acid or water-soluble oxalate, molybdic acid or water-soluble molybdate, water-soluble alkali earth metal salt and water-soluble europium salt, and the purpose that adds these raw materials is respectively to introduce oxalate denominationby, molybdenum acid ion, alkaline-earth metal ions and europium ion.Water-soluble oxalate, water-soluble molybdate, water-soluble alkali earth metal salt and water-soluble europium salt are that those of ordinary skills are known, for example comprise: potassium oxalate, ammonium oxalate and sodium oxalate; Sodium orthomolybdate, ammonium molybdate and potassium molybdate; Alkaline earth metal halide (being more preferably muriate), alkine earth metal nitrate and alkaline-earth metal acetate; Europium chloride, europium nitrate; But be not limited thereto.
The present inventor also finds, mixes at each raw material, uses less water as dispersion agent when grinding, and can promote speed of response and luminous intensity significantly.Used water is advisable not introduce impurity, can be distilled water, deionized water, redistilled water etc.The selected raw material of the present invention all has well water-soluble, grinds in the presence of less water, can chemical reaction take place quickly between mutually, generates water-fast double salt.
In addition, in using preparation method of the present invention, grinding better can be ball milling, and the adoptable rotating speed of ball milling is 100-250 rev/min, and good especially is 150 rev/mins.The time of grinding determines according to the consumption of raw material, was generally 0.5-2 hour, and better be 0.5 hour.On the other hand, because the strong grinding in each raw material reaction process is stirred, stoped growing up of double salt crystal grain, therefore prepared fluorescent material particle diameter is trickle.
Washing and filtering step among the preparation method of the present invention is used for removing to be introduced with raw material but not to be present in those ions in the final double salt, for example comprises: ammonium ion, sodium ion, potassium ion, chlorion, fluorion, acetate ion, nitrate ion etc.
Further specify the present invention by the following examples, but the present invention is not limited to these embodiment.
Embodiment 1
The CaCl of weighing 1.002mol 2, 0.132mol EuCl 3, 0.2mol Na 2MoO 4K with 1mol 2C 2O 4, put into the agate mortar grinding it is mixed, add 20 milliliters distilled water, continue to grind 0.5 hour, replace washing and filtering 3 times with distilled water and ethanol then, in 150 ℃ of oven dry, obtain rare-earth red fluorescent material.Determine the composition of this fluorescent material to be (Eu with X diffractometer and atomic absorption spectrometry 0.66Ca 0.01MoO 4) 0.2CaC 2O 4
This fluorescent material is further pulverized, sieved, obtain red fluorescence powder.Record the fluorescence spectrum figure of this fluorescent material with the Cary-E fluorescence spectrophotometer in room temperature, as shown in Figure 1.The curve on the left side is that wavelength is the fluorescent powder excitation line that records under the light monitoring of 614nm among Fig. 1; The curve on the right is to be the fluorescent material line of departure that the light of 265nm records as excitaton source with the wavelength.As shown in Figure 1, the fluorescence intensity of gained fluorescent material is 450a.u. in this example.
Gained fluorescent material was left standstill in air 90 days, redeterminate its fluorescence intensity, find that fluorescence intensity does not almost change.
Embodiment 2
Ca (the NO of weighing 1.028mol 3) 2, 0.168mol EuCl 3, 0.04mol (NH 4) 6Mo 7O 24(NH with 1mol 4) 2C 2O 4, put into the agate mortar grinding it is mixed, add 20 milliliters distilled water, continue to grind 45 minutes, replace washing and filtering 3 times with distilled water and ethanol then, in 100 ℃ of oven dry, obtain rare-earth red fluorescent material.Determine the composition of this fluorescent material to be (Eu with X diffractometer and atomic absorption spectrometry 0.6Ca 0.1MoO 4) 0.28CaC 2O 4
This fluorescent material is further pulverized, sieved, obtain red fluorescence powder.In this fluorescent material of indoor temperature measurement, its fluorescence emission spectrum is at the 614nm place with the Cary-E fluorescence spectrophotometer, and fluorescence intensity is 500a.u..Gained fluorescent material was left standstill in air 90 days, redeterminate its fluorescence intensity, find that fluorescence intensity does not almost change.
Embodiment 3
The Ca of weighing 1.0005mol (OAc) 2, 0.333mol Eu (NO 3) 3, 0.5mol H 2MoO 4H 2The Na of O and 1mol 2C 2O 4, ball milling made it mix in about 2 minutes in the adding ball mill, added 20 milliliters deionized water, continued ball milling 0.5 hour, replaced washing and filtering 3 times with distilled water and ethanol then, in 60 ℃ of oven dry, obtained rare-earth red fluorescent material.Determine the composition of this fluorescent material to be (Eu with X diffractometer and atomic absorption spectrometry 0.666Ca 0.001MoO 4) 0.5CaC 2O 4
This fluorescent material is further pulverized, sieved, obtain red fluorescence powder.In this fluorescent material of indoor temperature measurement, its fluorescence emission spectrum is at the 614nm place with the Cary-E fluorescence spectrophotometer, and fluorescence intensity is 450a.u..Gained fluorescent material was left standstill in air 90 days, redeterminate its fluorescence intensity, find that fluorescence intensity does not almost change.
Embodiment 4
The CaCl of weighing 1.0168mol 2, 0.2688mol Eu (NO 3) 3, 0.06mol (NH 4) 6Mo 7O 24(NH with 1mol 4) 2C 2O 4, put into the ball mill ball milling it is mixed, add 20 milliliters deionized water, continued ball milling 45 minutes, replace washing and filtering 3 times with distilled water and ethanol then, in 120 ℃ of oven dry, obtain rare-earth red fluorescent material.Determine the composition of this fluorescent material to be (Eu with X diffractometer and atomic absorption spectrometry 0.64Ca 0.04MoO 4) 0.42CaC 2O 4
This fluorescent material is further pulverized, sieved, obtain red fluorescence powder.In this fluorescent material of indoor temperature measurement, its fluorescence emission spectrum is at the 614nm place with the Cary-E fluorescence spectrophotometer, and fluorescence intensity is 480a.u..Gained fluorescent material was left standstill in air 90 days, redeterminate its fluorescence intensity, find that fluorescence intensity does not almost change.
Embodiment 5
The Ca of weighing 1.007mol (OAc) 2, 0.062mol Eu (NO 3) 3, 0.1mol Na 2MoO 4H with 1mol 2C 2O 42H 2O puts into the agate mortar grinding it is mixed, and adds 20 milliliters redistilled water, continues to grind 1 hour, replaces washing and filtering 3 times with distilled water and ethanol then, in 200 ℃ of oven dry, obtains rare-earth red fluorescent material.Determine the composition of this fluorescent material to be (Eu with X diffractometer and atomic absorption spectrometry 0.62Ca 0.07MoO 4) 0.1CaC 2O 4
This fluorescent material is further pulverized, sieved, obtain red fluorescence powder.In this fluorescent material of indoor temperature measurement, its fluorescence emission spectrum is at the 614nm place with the Cary-E fluorescence spectrophotometer, and fluorescence intensity is 450a.u..
Embodiment 6
The Ca of weighing 1.0021mol (OAc) 2, 0.1986mol EuCl 3, 0.3mol K 2MoO 4K with 1mol 2C 2O 4, put into agate mortar and ground 2 hours, replace washing and filtering 3 times with distilled water and ethanol then, in 150 ℃ of oven dry, obtain rare-earth red fluorescent material.Determine the composition of this fluorescent material to be (Eu with X diffractometer and atomic absorption spectrometry 0.662Ca 0.007MoO 4) 0.3CaC 2O 4
This fluorescent material is further pulverized, sieved, obtain red fluorescence powder.In this fluorescent material of indoor temperature measurement, its fluorescence emission spectrum is at the 614nm place with the Cary-E fluorescence spectrophotometer, and fluorescence intensity is 400a.u..Also can not make fluorescent material though do not add less water, its fluorescence intensity is lower.
Comparative example 1
Method by embodiment 1 is carried out, and different is to add ethanol to replace distilled water.In this fluorescent material of indoor temperature measurement, its fluorescence emission spectrum is at the 595nm place with the Cary-E fluorescence spectrophotometer, and fluorescence intensity is 200a.u..This shows that using ethanol only is about half of light-emitting phosphor intensity of the present invention as the luminous intensity of dispersion agent gained fluorescent material, and the fluorescent emission wavelength is also different.
Embodiment 7
Undertaken by embodiment 1 described identical method, different is to use SrCl 2Replaced C aClC 2, the gained rare-earth red fluorescent material consist of (Eu 0.66Sr 0.01MoO 4) 0.2SrC 2O 4Then, test, obtain similar fluorescence emission spectrum and fluorescence intensity by embodiment 1 described identical method.
Embodiment 8
Undertaken by embodiment 2 described identical methods, different is to use BaCl 2Replaced C a (NO 3) 2, the gained rare-earth red fluorescent material consist of (Eu 0.6Ba 0.1MoO 4) 0.28BaC 2O 4The gained fluorescent material is tested, obtained similar fluorescence emission spectrum and fluorescence intensity.
Embodiment 9
Undertaken by embodiment 6 described identical methods, different is with Mg (OAc) 2Replaced C a (OAc) 2, the gained rare-earth red fluorescent material consist of (Eu 0.662Mg 0.007MoO 4) 0.3MgC 2O 4The gained fluorescent material is tested, obtained similar fluorescence emission spectrum and fluorescence intensity.
Embodiment 10
Undertaken by embodiment 4 described identical methods, different is to use 0.5084mol CaCl 2With 0.5084mol MgCl 2Replace 1.0168mol CaCl 2, the gained rare-earth red fluorescent material consist of (Eu 0.64Ca 0.02Mg 0.02MoO 4) 0.42Ca 0.5Mg 0.5C 2O 4The gained fluorescent material is tested, obtained similar fluorescence emission spectrum and fluorescence intensity.

Claims (13)

1. rare-earth red fluorescent material, its composition is represented by following general formula:
(Eu 2(1-x)/3M xMoO 4) y·MC 2O 4
Wherein, M is the alkali earth metal that is selected from magnesium, calcium, strontium, barium or its combination, x=0.001-0.1, y=0.1-0.5.
2. rare-earth red fluorescent material as claimed in claim 1 is characterized in that M is a calcium.
3. rare-earth red fluorescent material as claimed in claim 1 is characterized in that x=0.01-0.1.
4. rare-earth red fluorescent material as claimed in claim 1 is characterized in that y=0.2-0.3.
5. method for preparing each described rare-earth red fluorescent material among the claim 1-4, this method comprises: mix oxalic acid or water-soluble oxalate, molybdic acid or water-soluble molybdate, water-soluble alkali earth metal salt and water-soluble europium salt as raw material, at room temperature water grinds as dispersion agent, washing and filtering, oven dry obtains rare-earth red fluorescent material.
6. method as claimed in claim 5 is characterized in that described method also comprises the step that the gained rare-earth red fluorescent material is pulverized and sieved.
7. as claim 5 or 6 described methods, it is characterized in that described water-soluble oxalate is selected from potassium oxalate, ammonium oxalate and sodium oxalate.
8. as claim 5 or 6 described methods, it is characterized in that described water-soluble molybdate is selected from Sodium orthomolybdate, ammonium molybdate and potassium molybdate.
9. as claim 5 or 6 described methods, it is characterized in that described water-soluble alkali earth metal salt is selected from alkaline earth metal halide, alkine earth metal nitrate and alkaline-earth metal acetate.
10. as claim 5 or 6 described methods, it is characterized in that described water-soluble europium salt is selected from europium chloride and europium nitrate.
11., it is characterized in that milling time is 0.5-2 hour as claim 5 or 6 described methods.
12., it is characterized in that bake out temperature is 60-200 ℃ as claim 5 or 6 described methods.
13. each described rare-earth red fluorescent material is in the purposes in following field among the claim 1-4: optical transfer agricultural film with light conversion agent, demonstration and illumination with fluorescent material, anti-fake fluorescent material and coating fluorescent material.
CN 02136995 2002-09-16 2002-09-16 rareearth red fluorescent material, its preparation method and use Expired - Fee Related CN1212366C (en)

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CN105087000B (en) * 2015-09-16 2017-02-22 温州大学 Oxalate luminescent material and preparation method thereof

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