CN1544576A - Long-time afterglow luminescent silicate material and its producing method - Google Patents
Long-time afterglow luminescent silicate material and its producing method Download PDFInfo
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- CN1544576A CN1544576A CNA2003101089226A CN200310108922A CN1544576A CN 1544576 A CN1544576 A CN 1544576A CN A2003101089226 A CNA2003101089226 A CN A2003101089226A CN 200310108922 A CN200310108922 A CN 200310108922A CN 1544576 A CN1544576 A CN 1544576A
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Abstract
The invention relates to a silicate steady persistence luminescent material and method for preparation whose constituents by weight percentage are CaO 23.70-24.47%, MgO 17.40-17.60%, SiO2 52.20-52.80%, B2O3 4.54-4.60%, Eu2O3 0.53-0.54%, Ln2O3 0-1.63%, wherein Ln is one or two element of Dy and Nd. The material according to the invention can be prepared through high temperature solid state reaction process comprising, first fully mixing CaCO3, 4MgCO3*Mg(OH)2*5H2O, SiO2 and fluxing medium H3BO3, charging Dy2O3 powder, Eu2O3 powder and Nd2O3 powder for mixed agglomeration 2-4 hours at 1200-1400 deg. C in reduction atmosphere, , disintegrating the burned materials and sieving to obtain the luminescent powder with relative graininess.
Description
Technical field
What the present invention relates to is a kind of long after glow luminous material and preparation method thereof, and particularly a kind of long persistence luminescent silicate material and preparation method thereof belongs to the material field.
Background technology
Traditional sulfide series long after glow luminous material is through constantly improving, formed several typical products, as: ZnS:Cu (green emitting), (CaSr) S:Bi (blue look luminous), (ZnCd) S:Cu (yellow orange is luminous), but the shortcoming of this class material is a poor stability, easily decomposes in air, and variable ash is to black under solar radiation, luminous time of persistence is short, in 0.5-2 hour, and luminosity is on the low side, does not satisfy practical requirement.Be to improve the luminosity of material, prolong time of persistence, people successively in this class material, added Co, Ra,
3Radioelement such as H have been made the radioluminescence long-afterglow material, though make material sustainable luminous and be applied to instrument, clock field, because radioactive pollution and costing an arm and a leg, use range is subjected to very big restriction.Since the nineties, aluminate long after glow luminous material is as a kind of energy-conservation energy storage material, because the luminosity that it is high, good steady persistence performance and stable preferably makes it be applied at aspects such as daily necessities, low illumination Pointing sign board, clock and watch.
Find that by literature search Chinese patent application number is 97121964.8, publication number is: 1188788, and name is called: a kind of light-accumulative luminous material and preparation method thereof, this patent disclosure: the chemical constitution of aluminate long after glow luminous material is MOAl
2O
3: Eu, N, wherein M represents Sr or Ga, and N represents Dy or Sm.The preparation method adopts the oxide compound of aluminium, strontium, calcium, boron, perhaps through adding the salt that heat energy produces above-mentioned oxide compound, by each elementary composition in its chemical constitution formula than concerning weighing, adding is with 1～10% carbon dust of volume, and for reducing the boric acid ground and mixed of temperature of reaction adding 1～10%, seal behind the sealed vessel of again mixture being packed into, calcining is 10 minutes～6 hours in 1420～1600 ℃ of High Temperature Furnaces Heating Apparatuss, after taking out cooling, pulverize.There are some shortcomings in this class material, and as poor water resistance, the higher and glow color of production energy consumption is single etc., can not satisfy the requirement to long after glow luminous material to a certain extent well.And this preparation method makes to obtain the product performance poor stability owing to add carbon dust and mix, and purity is low.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, a kind of long persistence luminescent silicate material and preparation method thereof is provided, make its preparation method easy, material afterglow performance improves, thereby has solved the defective in the background technology.
The present invention is achieved through the following technical solutions.Material of the present invention is to be matrix with silicate, and rare earth ion and other ion are activator, and by the long after glow luminous material that the compound that adds boracic facilitates the steady persistence performance to improve, its chemical constitution formula is: Ca
0.973OMgO (SiO
2)
20.15B
2O
3: Eu
0.007, Ln
0.02, its its weight percent CaO:23.70～24.47%, MgO:17.40～17.60%, SiO
2: 52.20～52.80%, B
2O
3: 4.54～4.60%, Eu
2O
3: 0.53～0.54%, Ln
2O
3: 0～1.63%.Wherein Ln is one or both elements among Dy or the Nd.
The crystalline structure of material of the present invention is the diopside structure of monocline, and its chemical formula is CaMgSi
2O
6, use Eu
2+As exciting agent, Nd
3+, Dy
3+For being total to exciting agent, high-temperature calcination obtains blue long afterflow luminescent material under carbon reduction atmosphere.
Long persistence luminescent silicate material of the present invention prepares by high temperature solid state reaction technology, at first with CaCO
3, 4MgCO
3Mg (OH)
25H
2O and SiO
2, and fusing assistant H
3BO
3Thorough mixing adds Dy again
2O
3Powder, Eu
2O
3Powder and Nd
2O
3The powder mixing is burnt till, and sintering carries out in reducing atmosphere, at 1200～1400 ℃ of sintering 2-4 hours, burns till the back material through pulverizing and sieving, and can obtain the luminescent powder of corresponding granularity.
Below the inventive method is further specified, concrete steps are as follows:
(1) carry out proportioning raw materials, raw material adopts chemical pure CaCO
3, 4MgCO
3Mg (OH)
25H
2O, SiO
2, Eu
2O
3, Dy
2O
3, Nd
2O
3, carry out proportioning by its component, and add the H of 15% mol ratio
3BO
3As fusing assistant;
(2) with above-mentioned raw materials wet ball grinding 4 hours, powder is mixed, adopt ethanol, these organic solvents of acetone when ball milling mixes, discharging and oven dry behind the ball milling as ball-milling medium;
(3) use carbon dust as reductive agent, it is made airtight canister, said mixture is packed into to seal in the canister to be sealed, and puts into the crucible of airtight aluminum oxide.Calcination 2～4 hours in 1200～1400 ℃ of High Temperature Furnaces Heating Apparatuss then, take out cooling after, crushing screening gets long persistence luminescent silicate material.
Luminescent material of the present invention can mix in plastics, resin, printing ink, the paint, directly makes or applies on the ornament or sign class of formation; Also it can be mixed in the ceramic glaze, directly be fired into luminescent ceramic, through fluorescent lamp or natural light irradiation and become light emitting display body.
Compared with prior art, the present invention adopts this novel long persistence luminescent silicate material of high temperature solid state reaction prepared, its preparation method is easy, the long after glow luminous material that makes, its material has excellent water tolerance energy and stability, put it in the water, do not see decomposition after three months yet, still as seen luminous.
Embodiment
Provide following examples below in conjunction with content of the present invention, embodiment does further statement to the present invention.
Embodiment 1, CaOMgO2SiO
20.15B
2O
3: Eu
0.007Long after glow luminous material
Proportioning raw materials as shown in Table 1.
Table one: CaOMgO2SiO
20.15B
2O
3: Eu
0.007The proportioning of long-afterglow luminescent powder
| Component | Weight percent | Raw material | Quantity |
| ????CaO | ????24.47％ | ????CaCO 3 | 99.3 gram |
| ????MgO | ????17.60％ | ??4MgCO 3·Mg(OH) 2·5H 2O | 97.16 gram |
| ????SiO 2 | ????52.80％ | ????SiO 2 | 120 grams |
| ????B 2O 3 | ????4.60％ | ????H 3BO 3 | 18.54 gram |
| ????Eu 2O 3 | ????0.53％ | ????Eu 2O 3 | 1.23 gram |
After porphyrize mixes oven dry in ethanolic soln with above-mentioned batching, insert in the canister, the alumina crucible of packing into is put into High Temperature Furnaces Heating Apparatus 1250 ℃ of sintering 4 hours, and cooling is pulverized burned material again, and 200 eye mesh screens sieve, and make example materials.
This example materials outward appearance is white in color.With the XRD test, show that its structure is monoclinic diopside structure, its phase composite is CaMgSi
2O
6After sunlight or uviolizing, it is luminous in the dark to present blue colour excess brightness; After light source was removed, this material was at the discernmible luminosity (0.32mcd/m of human eye
2) above can also be luminous more than 6 hours.Example materials is carried out spectrum test, and its emission wavelength is positioned at the 438nm place.This luminescent powder is immersed in the water, takes out after three months, after the oven dry, under light source activation, can observe obvious afterglow.
Embodiment 2
CaOMgO2SiO
20.15B
2O
3: Eu
0.007, Nd
0.02Long after glow luminous material
Proportioning raw materials as shown in Table 2.
Table two: CaOMgO2SiO
20.15B
2O
3: Eu
0.007, Nd
0.02The proportioning of long-afterglow luminescent powder
| Component | Weight percentage | Raw material | Quantity |
| ????CaO | ????23.74％ | ????CaCO 3 | 97.3 gram |
| ????MgO | ????17.43％ | ?4MgCO 3·Mg(OH) 2·5H 2O | 97.16 gram |
| ????SiO 2 | ????52.28％ | ????SiO 2 | 120 grams |
| ????B 2O 3 | ????4.55％ | ????H 3BO 3 | 18.54 gram |
| ????Eu 2O 3 | ????0.54％ | ????Eu 2O 3 | 1.23 gram |
| ????Nd 2O 3 | ????1.46％ | ????Nd 2O 3 | 3.36 gram |
Above-mentioned batching porphyrize in ethanol medium is mixed, dry after the discharging, insert in the canister, the alumina crucible of packing into is put into High Temperature Furnaces Heating Apparatus 1250 ℃ of calcinings 4 hours, and cooling is pulverized burned material again, and 200 eye mesh screens sieve, and make example materials.
This example materials outward appearance is white in color.With the XRD test, show that its structure is the diopside structure of monocline, its main compound is CaMgSi
2O
6According to its main compound, determine the chemical expression formula CaMgSi of material
2O
6: Eu, Nd.After sunlight or uviolizing, it is luminous to present blue colour excess brightness, and after light source was removed, its twilight sunset luminous intensity values was apparently higher than embodiment 1.This material is at the discernmible luminosity (0.32mcd/m of human eye
2) above can also be luminous more than 10 hours.Example materials is carried out spectrum test, and its emission wavelength is positioned at the 438nm place.This luminescent powder is immersed in the water, takes out after three months, after the oven dry, under light source activation, can observe blue afterglow.
Embodiment 3
CaOMgO2SiO
20.15B
2O
3: Eu
0.007, Dy
0.02Synthetic and the analytical results of material
Proportioning raw materials is as shown in Table 3:
Table three: CaOMgO2SiO
20.15B
2O
3: Eu
0.007, Dy
0.02The proportioning of long-afterglow luminescent powder
| Component | Weight percentage | Raw material | Quantity |
| ????CaO | ????23.70％ | ????CaCO 3 | 97.3 gram |
| ????MgO | ????17.40％ | ??4MgCO 3·Mg(OH) 2·5H 2O | 97.16 gram |
| ????SiO 2 | ????52.20％ | ????SiO 2 | 120 grams |
| ????B 2O 3 | ????4.54％ | ????H 3BO 3 | 18.54 gram |
| ????Eu 2O 3 | ????0.53％ | ????Eu 2O 3 | 1.23 gram |
| ????Dy 2O 3 | ????1.63％ | ????Dy 2O 3 | 3.73 gram |
After porphyrize mixes oven dry in ethanol medium with above-mentioned batching, insert in the canister, the alumina crucible of packing into is put into High Temperature Furnaces Heating Apparatus 1250 ℃ of calcinings 4 hours, and cooling is pulverized burned material again, and 200 eye mesh screens sieve, and make example materials.
This example materials outward appearance is white in color.With the XRD test, show that its structure is the diopside structure of monocline, its main compound is CaMgSi
2O
6According to its main compound, determine the chemical expression formula CaMgSi of material
2O
6: Eu, Dy.After sunlight or uviolizing, visible tangible blue colour excess brightness is luminous, and after light source was removed, its twilight sunset luminous intensity values was apparently higher than embodiment 1 and embodiment 2.This material is at the discernmible luminosity (0.32mcd/m of human eye
2) above can continue luminous more than 12 hours.This example materials is carried out spectrum test, and its emission wavelength is positioned at the 436nm place.This luminescent powder is immersed in the water, takes out after three months, after the oven dry, under light source activation, can observe obvious blue afterglow.
Claims (5)
1, a kind of long persistence luminescent silicate material is characterized in that, its chemical formula is: Ca
0.973OMgO (SiO
2)
20.15B
2O
3: Eu
0.007, Ln
0.02, its weight percent CaO:23.70～24.47%, MgO:17.40～17.60%, SiO
2: 52.20～52.80%, B
2O
3: 4.54～4.60%, Eu
2O
3: 0.53～0.54%, Ln
2O
3: 0～1.63%, wherein Ln is one or both elements among Dy or the Nd.
2, long persistence luminescent silicate material according to claim 1 is characterized in that, the crystalline structure of material is the diopside structure of monocline, and its chemical formula is CaMgSi
2O
6, use Eu
2+As exciting agent, Nd
3+, Dy
3+For being total to exciting agent, high-temperature calcination obtains blue long afterflow luminescent material under carbon reduction atmosphere.
3, long persistence luminescent silicate material according to claim 1, it is characterized in that, mix in plastics, resin, printing ink, the paint, directly make or apply on the ornament or sign class of formation, perhaps it is mixed in the ceramic glaze, directly be fired into luminescent ceramic, through fluorescent lamp or natural light irradiation and become light emitting display body.
4, a kind of preparation method of long persistence luminescent silicate material is characterized in that, prepares by high temperature solid state reaction technology, at first with CaCO
3, 4MgCO
3Mg (OH)
25H
2O and SiO
2, and fusing assistant H
3BO
3Thorough mixing adds Dy again
2O
3Powder, Eu
2O
3Powder and Nd
2O
3The powder mixing is burnt till, and sintering carries out in reducing atmosphere, at 1200～1400 ℃ of sintering 2-4 hours, burns till the back material through pulverizing and sieving, and can obtain the luminescent powder of corresponding granularity.
5, the preparation method of long persistence luminescent silicate material according to claim 4 below is further qualified the inventive method, and concrete steps are as follows:
(1) carry out proportioning raw materials, raw material adopts chemical pure CaCO
3, 4MgCO
3Mg (OH)
25H
2O, SiO
2, Eu
2O
3, Dy
2O
3, Nd
2O
3, carry out proportioning by its component, and add the H of 15% mol ratio
3BO
3As fusing assistant;
(2) with above-mentioned raw materials wet ball grinding 4 hours, powder is mixed, adopt ethanol, these organic solvents of acetone when ball milling mixes, discharging and oven dry behind the ball milling as ball-milling medium;
(3) use carbon dust as reductive agent, it is made airtight canister, and put into the crucible of airtight aluminum oxide, the said mixture sealing of packing into is sealed in the canister, in reducing atmosphere, carry out sintering then, i.e. calcination 2～4 hours in 1200～1400 ℃ of High Temperature Furnaces Heating Apparatuss, take out cooling after, crushing screening gets long persistence luminescent silicate material.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101089226A CN1325603C (en) | 2003-11-27 | 2003-11-27 | Long-time afterglow luminescent silicate material and its producing method |
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| Publication Number | Publication Date |
|---|---|
| CN1544576A true CN1544576A (en) | 2004-11-10 |
| CN1325603C CN1325603C (en) | 2007-07-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739610A (en) * | 2017-11-02 | 2018-02-27 | 杭州显庆科技有限公司 | A kind of yellow longpersistent fluorescent material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951915A (en) * | 1996-01-22 | 1999-09-14 | Kasei Optonix, Ltd. | Phosphorescent phosphor |
| CN1186103A (en) * | 1996-12-26 | 1998-07-01 | 中国科学院长春物理研究所 | Green fluorescent powder and preparation thereof |
| ES2230623T3 (en) * | 1997-03-26 | 2005-05-01 | Zhiguo Xiao | SILICATE LUMINISCENT MATERIAL WITH LONG-TERM POSTLUMINISCENCE AND MANUFACTURING PROCEDURE OF THE SAME. |
| CN1062581C (en) * | 1997-03-26 | 2001-02-28 | 肖志国 | Long persistence luminescent silicate material and its producing method |
| CN1192077C (en) * | 1999-04-09 | 2005-03-09 | 肖志国 | Luminous jade and preparing process thereof |
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Cited By (3)
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| CN107739610A (en) * | 2017-11-02 | 2018-02-27 | 杭州显庆科技有限公司 | A kind of yellow longpersistent fluorescent material and preparation method thereof |
| CN107739610B (en) * | 2017-11-02 | 2018-12-04 | 慈溪飞诺斯电子科技有限公司 | A kind of yellow longpersistent fluorescent powder and preparation method thereof |
| CN108949164A (en) * | 2017-11-02 | 2018-12-07 | 王小琴 | A kind of yellow longpersistent light-emitting component |
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Granted publication date: 20070711 Termination date: 20091228 |