CN1974715A - Prepn of nanometer spherical red CaSiO3:Eu3+ phosphor - Google Patents
Prepn of nanometer spherical red CaSiO3:Eu3+ phosphor Download PDFInfo
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- CN1974715A CN1974715A CN 200610147489 CN200610147489A CN1974715A CN 1974715 A CN1974715 A CN 1974715A CN 200610147489 CN200610147489 CN 200610147489 CN 200610147489 A CN200610147489 A CN 200610147489A CN 1974715 A CN1974715 A CN 1974715A
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- reverse micelle
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Abstract
The preparation of nanometer RE red phosphor is disclosed. The nanometer RE red phosphor has the chemical expression of Ca2-xSiO3:Eux, where, x is 0-0.05. The preparation process features using Ca(NO3)2 and Na2SiO3 as the material for synthesizing matrix, europia as material dissolved in nitric acid to prepare europium nitrate serving as the fluorescent activating source, and non-ionic surfactant XL80 forming in cyclohexane spherical reverse micelle serving as soft template. The preparation process includes the steps of compounding two portions of cyclohexane solution of XL80 in the same volume and concentration, adding 0.3 mol/L concentration of Ca(NO3)2 solution containing Eu3+ to one portion of the solution and 0.3 mol/L concentration of Na2SiO3 solution containing Eu3+ to the other, controlling size of water nucleus and magnetically stirring to obtain reverse micelle systems, mixing via drastic stirring, demulsifying, centrifugally separating, drying precipitate and roasting.
Description
Technical field
The present invention relates to a kind of making method of rare earth luminescent material, refer in particular to a kind of CaSiO
3: Eu
3+The preparation of nanometer spherical red fluorescent material.
Background technology silicate is a kind of good luminescent material matrix because of its excellent chemical stability and thermostability.After mixing transition metal ion or rare earth ion, has higher luminous efficiency.Eu
3+Ionic red emission function has been widely used in color TV, flat pannel display, cathode tube and the three primary colors fluorescent powder, CaSiO
3: Eu
3+The existing synthetic and research of fluorescent material, but the preparation method who generally adopts at present is a high temperature solid-state method.But the fluorescent material powder sintering phenomenon that high temperature solid-state method is made is serious, needs repeatedly can drop into application after ball milling, the screening.Thereby exist the particle particle big, be difficult to deficiencies such as miniaturization, dispersion effect and microscopic appearance be relatively poor.Luminescent properties and its form based on luminescent material have much relations, and spheroidal particle can improve its close heap, thereby improve its luminosity.In addition, fluorescent material is coated with the requirement of shielding technology and also presses for synthesizing spherical fluorescent material.
Summary of the invention
Purpose of the present invention: be intended to propose a kind of new preparation method and prepare nanometer spherical rare earth silicate red fluorescence powder.
The manufacture method of this rare earth nano red-emitting phosphors, its chemical expression is as follows: Ca
2-xSiO
3: Eu
x0≤x≤0.05 wherein is characterized in that:
A, it is with Ca (NO
3)
2And Na
2SiO
3As the raw material of synthetic substrate, as raw material, and make europium nitrate as the fluorescence-activation source with europium sesquioxide with nitric acid dissolve, with nonionogenic tenside XL80 in hexanaphthene, form spherical reverse micelle and with this as soft template;
B, its making method are: prepare respectively that two parts of volumes are identical, concentration is the cyclohexane solution of the XL80 of 0.2mol/L, add equivalent 0.3mol/L respectively and contain Eu
3+Ca (NO
3)
2Solution and 0.3mol/LNa
2SiO
3Solution, control water nuclear size makes the reverse micelle system of clear through magnetic agitation, again two inverse micellar solutions mixed, breakdown of emulsion, centrifugation after the vigorous stirring, collecting precipitation drying, roasting then promptly gets sample.
Water is examined big or small w in its reverse micelle
0Value is 5,10 (w
0Amount of substance ratio for water and tensio-active agent).
Drying temperature when dry is 70 ℃, and the thermal treatment temp of use is at 500～700 ℃.
Used Eu
3+The mole doping content be 1-5%.
At least 1 hour time during magnetic agitation, the time of vigorous stirring was at least 24 hours.
The present invention adopts the reverse micelle soft template method to prepare the CaSiO that particle diameter is less, have the spheroid pattern
3: Eu
3+The red nano-fluorescent powder material.Notable attribute is that preparation two parts of equal-volumes, concentration are the cyclohexane solution of the XL80 of 0.2mol/L, and the 0.3mol/L that joins equivalent respectively contains Eu
3+Ca (NO
3)
2Solution and 0.3mol/L Na
2SiO
3In the solution, by changing Ca (NO
3)
2/ Eu
3+Solution and Na
2SiO
3The size in the adding volume control pond of solution, magnetic agitation obtains the reverse micelle system of clear.Again two inverse micellar solutions are mixed rapidly under the normal temperature, after vigorous stirring reaction for some time, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to treat to discard supernatant liquid after the layering centrifugation collecting precipitation drying.Promptly obtain desired fluorescent material behind the sintering.This fluorescent material has stronger excitation peak at the 350-450nm place, and wherein the strongest excitation wavelength is at the 395nm place, and corresponding emission main peak is the red emission at 613nm place; Has tangible use superiority.For the nano luminescent material for preparing special appearance provides a new approach, the nanometer spherical CaSiO for preparing
3: Eu
3+Luminescent material is the good rare-earth red fluorescent material of a kind of application performance.
Description of drawings
The CaSiO that accompanying drawing 1 is made for present method
3: Eu
3+Nanometer spherical red fluorescent material mirror phase morphology figure;
Accompanying drawing 2 is CaSiO
3: Eu
3+The XRD figure spectrum of nanometer spherical red fluorescent material;
Accompanying drawing 3 is CaSiO
3: Eu
3+The excitation spectrum of nanometer spherical red fluorescent material and emmission spectrum figure.
Embodiment
Embodiment 1
Take by weighing 0.528gEu
2O
3, add HNO
3Dissolving obtains Eu (NO
3)
3And evaporative crystallization, take by weighing 7.084gCa (NO again
3)
24H
2O adds Eu (NO
3)
3With dissolved in distilled water, 100mL volumetric flask constant volume is mixed with and contains Eu
3+The mole doping content is 1% 0.3mol/L Ca (NO
3)
2Solution.Cofabrication 0.3mol/L Na
2SiO
3Solution.
Prepare two parts of 200mL, the XL80/ cyclohexane solution of 0.2mol/L adds 0.3mol/LCa (NO respectively
3)
2(contain 1mol%Eu
3+) solution and 0.3mol/L Na
2SiO
3Each 3.6mL of solution, magnetic agitation 1h makes the reverse micelle system of clear, w
0Value is 5 (w
0Amount of substance ratio for water and tensio-active agent).Under the normal temperature two inverse micellar solutions are mixed rapidly then, behind the vigorous stirring 24h, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to make its layering, discard supernatant liquid, the centrifugation collecting precipitation is in 70 ℃ of dry 4h.In 700 ℃ of roasting 2h, take out the cooling back, places moisture eliminator standby again.
Embodiment 2
Take by weighing 0.053gEu
2O
3, add HNO
3Dissolving obtains Eu (NO
3)
3And evaporative crystallization, take by weighing 7.084gCa (NO again
3)
24H
2O adds Eu (NO
3)
3With dissolved in distilled water, 100mL volumetric flask constant volume is mixed with and contains Eu
3+The mole doping content is 0.1% 0.3mol/L Ca (NO
3)
2Solution.Cofabrication 0.3mol/L Na
2SiO
3Solution.
Prepare two parts of 200mL, the XL80/ cyclohexane solution of 0.2mol/L adds 0.3mol/LCa (NO respectively
3)
2(contain 0.1mol%Eu
3+) solution and 0.3mol/L Na
2SiO
3Each 7.2mL of solution, magnetic agitation 1h makes the reverse micelle system of clear, w
0Value is 10.Under the normal temperature two inverse micellar solutions are mixed rapidly then, behind the vigorous stirring 24h, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to make its layering, discard supernatant liquid, the centrifugation collecting precipitation is in 70 ℃ of dry 4h.In 500 ℃ of roasting 2h, take out the cooling back, places moisture eliminator standby again.
Take by weighing 1.056gEu
2O
3, add HNO
3Dissolving obtains Eu (NO
3)
3And evaporative crystallization, take by weighing 7.084gCa (NO again
3)
24H
2O adds Eu (NO
3)
3With dissolved in distilled water, 100mL volumetric flask constant volume is mixed with and contains Eu
3+The mole doping content is 2% 0.3mol/L Ca (NO
3)
2Solution.Cofabrication 0.3mol/L Na
2SiO
3Solution.
Prepare two parts of 200mL, the XL80/ cyclohexane solution of 0.2mol/L adds 0.3mol/LCa (NO respectively
3)
2(contain 2mol%Eu
3+) solution and 0.3mol/L Na
2SiO
3Each 3.6mL of solution, magnetic agitation 1h makes the reverse micelle system of clear, w
0Value is 5.Under the normal temperature two inverse micellar solutions are mixed rapidly then, behind the vigorous stirring 24h, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to make its layering, discard supernatant liquid, the centrifugation collecting precipitation is in 70 ℃ of dry 4h.In 600 ℃ of roasting 2h, take out the cooling back again, grinds evenly to place moisture eliminator standby.
Embodiment 4
Take by weighing 1.583gEu
2O
3, add HNO
3Dissolving obtains Eu (NO
3)
3And evaporative crystallization, take by weighing 7.084gCa (NO again
3)
24H
2O adds Eu (NO
3)
3With dissolved in distilled water, 100mL volumetric flask constant volume is mixed with and contains Eu
3+The mole doping content is 3% 0.3mol/L Ca (NO
3)
2Solution.Cofabrication 0.3mol/L Na
2SiO
3Solution.
Prepare two parts of 200mL, the XL80/ cyclohexane solution of 0.2mol/L adds 0.3mol/LCa (NO respectively
3)
2(contain 3mol%Eu
3+) solution and 0.3mol/L Na
2SiO
3Each 3.6mL of solution, magnetic agitation 1h makes the reverse micelle system of clear, w
0Value is 5.Under the normal temperature two inverse micellar solutions are mixed rapidly then, behind the vigorous stirring 24h, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to make its layering, discard supernatant liquid, the centrifugation collecting precipitation is in 70 ℃ of dry 4h.In 700 ℃ of roasting 2h, take out the cooling back again, grinds evenly to place moisture eliminator standby.
Embodiment 5
Take by weighing 2.111gEu
2O
3, add HNO
3Dissolving obtains Eu (NO
3)
3And evaporative crystallization, take by weighing 7.084gCa (NO again
3)
24H
2O adds Eu (NO
3)
3With dissolved in distilled water, 100mL volumetric flask constant volume is mixed with and contains Eu
3+The mole doping content is 4% 0.3mol/L Ca (NO
3)
2Solution.Cofabrication 0.3mol/L Na
2SiO
3Solution.
Prepare two parts of 200mL, the XL80/ cyclohexane solution of 0.2mol/L adds 0.3mol/LCa (NO respectively
3)
2(contain 4mol%Eu
3+) solution and 0.3mol/L Na
2SiO
3Each 3.6mL of solution, magnetic agitation 1h makes the reverse micelle system of clear, w
0Value is 5.Under the normal temperature two inverse micellar solutions are mixed rapidly then, behind the vigorous stirring 24h, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to make its layering, discard supernatant liquid, the centrifugation collecting precipitation is in 70 ℃ of dry 4h.In 700 ℃ of roasting 2h, take out the cooling back again, grinds evenly to place moisture eliminator standby.
Embodiment 6
Take by weighing 2.639gEu
2O
3, add HNO
3Dissolving obtains Eu (NO
3)
3And evaporative crystallization, take by weighing 7.084gCa (NO again
3)
24H
2O adds Eu (NO
3)
3With dissolved in distilled water, 100mL volumetric flask constant volume is mixed with and contains Eu
3+The mole doping content is 5% 0.3mol/L Ca (NO
3)
2Solution.Cofabrication 0.3mol/L Na
2SiO
3Solution.
Prepare two parts of 200mL, the XL80/ cyclohexane solution of 0.2mol/L adds 0.3mol/LCa (NO respectively
3)
2(contain 5mol%Eu
3+) solution and 0.3mol/L Na
2SiO
3Each 3.6mL of solution, magnetic agitation 1h makes the reverse micelle system of clear, w
0Value is 5.Under the normal temperature two inverse micellar solutions are mixed rapidly then, behind the vigorous stirring 24h, add the dehydrated alcohol breakdown of emulsion, leave standstill for some time to make its layering, discard supernatant liquid, the centrifugation collecting precipitation is in 70 ℃ of dry 4h.In 700 ℃ of roasting 2h, take out the cooling back again, grinds evenly to place moisture eliminator standby.
Claims (5)
1, a kind of manufacture method of rare earth nano red-emitting phosphors is characterized in that:
A, its chemical expression are as follows: Ca
2-xSiO
3: Eu
x0≤x≤0.05 wherein;
B, it is with Ca (NO
3)
2And Na
2SiO
3As the raw material of synthetic substrate, as raw material, and make europium nitrate as the fluorescence-activation source with europium sesquioxide with nitric acid dissolve, with nonionogenic tenside XL80 in hexanaphthene, form spherical reverse micelle and with this as soft template;
C, its making method are: prepare the cyclohexane solution of two parts of volumes, XL80 that concentration is all identical respectively, add equivalent 0.3mol/L respectively and contain Eu
3+Ca (NO
3)
2Solution and 0.3mol/LNa
2SiO
3Solution, control water nuclear size makes the reverse micelle system of clear through magnetic agitation, again two inverse micellar solutions mixed, breakdown of emulsion, centrifugation after the vigorous stirring, collecting precipitation drying, roasting then promptly gets sample.
2, the manufacture method of a kind of rare earth nano red-emitting phosphors as claimed in claim, it is characterized in that: water is examined big or small w in the reverse micelle
0Value is 5,10 (w
0Amount of substance ratio for water and tensio-active agent).
3, the manufacture method of a kind of rare earth nano red-emitting phosphors as claimed in claim is characterized in that: drying temperature is 70 ℃, and the thermal treatment temp of use is at 500～700 ℃.
4, the manufacture method of a kind of rare earth nano red-emitting phosphors as claimed in claim is characterized in that: Eu
3+The mole doping content be 1-5%.
5, the manufacture method of a kind of rare earth nano red-emitting phosphors as claimed in claim is characterized in that: at least 1 hour time of magnetic agitation, the time of vigorous stirring was at least 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101474890A CN100503775C (en) | 2006-12-19 | 2006-12-19 | Preparation of nanometer spherical red CaSiO3:Eu3+ phosphor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101474890A CN100503775C (en) | 2006-12-19 | 2006-12-19 | Preparation of nanometer spherical red CaSiO3:Eu3+ phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1974715A true CN1974715A (en) | 2007-06-06 |
| CN100503775C CN100503775C (en) | 2009-06-24 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643643B (en) * | 2009-02-05 | 2011-12-07 | 西南科技大学 | Preparation method for low-temperature synthetic calcium carbonate-based red lanthanide luminescent material |
| CN101735804B (en) * | 2009-12-11 | 2012-07-04 | 四川大学 | Blue fluorescent powder for white-light LED and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313919A (en) * | 2014-10-09 | 2015-01-28 | 西南大学 | Non-ionic mixed reversed micelles and preparation method thereof |
-
2006
- 2006-12-19 CN CNB2006101474890A patent/CN100503775C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643643B (en) * | 2009-02-05 | 2011-12-07 | 西南科技大学 | Preparation method for low-temperature synthetic calcium carbonate-based red lanthanide luminescent material |
| CN101735804B (en) * | 2009-12-11 | 2012-07-04 | 四川大学 | Blue fluorescent powder for white-light LED and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100503775C (en) | 2009-06-24 |
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Granted publication date: 20090624 Termination date: 20111219 |