CN1266250C - Orange long persistence fluorescent material and its production - Google Patents
Orange long persistence fluorescent material and its production Download PDFInfo
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- CN1266250C CN1266250C CN 200410020722 CN200410020722A CN1266250C CN 1266250 C CN1266250 C CN 1266250C CN 200410020722 CN200410020722 CN 200410020722 CN 200410020722 A CN200410020722 A CN 200410020722A CN 1266250 C CN1266250 C CN 1266250C
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Abstract
The present invention discloses an orange yellow long afterglow luminescent material whose chemical constitution is aY2O2S: bTi<4+> and cMg<2+>, wherein a is greater than or equal to 0.9 mole fraction and is smaller than or equal to 0.99 mole fraction, b is greater than or equal to 0.01 mole fraction and is smaller than or equal to 0.1, and c is greater than or equal to 0.01 mole fraction and is smaller than or equal to 0.05 mole fraction. A production method of the material comprises: yttrium oxide Y2O3, compounds containing Ti<4+>, compounds containing Mg<2+>, sulphur and sodium carbonate Na2CO3 are used as raw materials, and carbon is used as a reducing agent; the raw materials have the following compounding ratios: 0.9 to 0.99 mole fraction of yttrium oxide Y2O3, 0.01 to 0.1 mole fraction of Ti<4+>, 0.01 to 0.05 mole fraction of Mg<2+>, 30 to 40% of sulphur of the total mass and 30 to 40% of sodium carbonate Na2CO3 of the total mass, and the weight of the carbon is from 1/4 to 1/2 of the mass of loaded materials; the raw materials are mixed and are ignited for 3 to 6 hours at 200 to 500 DEG C under a reduction condition; then, the raw materials are ignited for 1 to 3 hours at 1100 to 1300 DEG C under the reduction condition; after being soaked for 2 to 3 hours in hot water at 75 to 85 DEG C, obtained products are dried after being washed with hot water. The present invention has the advantages of low product cost and environmental protection of production technologies.
Description
The technical field is as follows:
the invention relates to a long afterglow luminescent material and a production method thereof, in particular to an orange yellow long afterglow luminescent material and a production method thereof.
Background art:
in the early 90 s, two major long-afterglow luminescent materials, namely an aluminate system and a silicate system, are invented successively, and are improved in the aspects of luminous brightness, afterglow time and chemical stability compared with the long-afterglow luminescent materials of the traditional zinc sulfate system, but the luminescent colors of the two major long-afterglow luminescent materials are generally yellow green, blue purple and blue green and are difficult to meet the requirements. In the future, the invention provides red, orange-red long afterglow luminescent materials and orange-yellow long afterglow luminescent materials. The chemical compositions of the red and orange-red long afterglow luminescent materials are Ms: Eu, Tm, Ms: Eux，Ay，BzBut the afterglow time is only tens of minutes, the chemical property is unstable, and the water is easy to hydrolyze. The chemical compositions of the orange-yellow long-afterglow luminescent material are basically two types: one is ZnS, Mn and Cu, which has the disadvantages of low luminous intensity, short afterglow time, unstable chemical property, easy decomposition in air, easy hydrolysis and the like, although some radioactive elements are added in the material to increase the luminous brightness and prolong the afterglow time, the radioactive elements pollute the environment and are harmful to human bodies, so the application of the radioactive elements is greatly limited; still another technology closest to the present patent application is the technology of the patent application with Chinese patent application No. 02188548.4 entitled "orange yellow emitting rare earth long persistence phosphor". The patent application discloses yttrium oxysulfide (Y)2O2S) is taken as a substrate, trivalent thulium ions are taken as active ions, divalent magnesium ions and tetravalent titanium ions are taken as additive ions, and sodium carbonate is taken as a cosolvent. The production method comprises the steps of firing for 5-6 hours at the temperature of 1000-1150 ℃ in the reducing atmosphere of activated carbon, taking the product out of the furnace at high temperature, soaking in hot hydrochloric acid for 1.5-2 hours, washing with hot water, and drying to obtain the product. Despite thisThe long afterglow phosphor has superior luminous intensity and afterglow time to ZnS series products, stable chemical property and uneasy hydrolysis, but the products and the production method have the following disadvantages: the raw materials contain rare earth ion thulium which is expensive, so that the raw material cost of the product is high; the long-time high-temperature heating in the production process not only wastes a large amount of energy, but also increases the manufacturing cost of the product; when the product is soaked by hot hydrochloric acid, harmful hydrogen sulfide gas is generated.
The invention content is as follows:
the invention provides an orange-yellow long-afterglow luminescent material which has low product cost, energy conservation and environmental protection and a production method thereof, and aims to solve the technical problems of high product cost, energy waste, environmental pollution and the like in the prior art.
The technical solution of the invention is as follows: an orange-yellow long afterglow luminescent material is characterized by comprising the following chemical components: aY2O2S:bTi4+，cMg2+Wherein a is more than or equal to 0.9 and less than or equal to 0.99 mol, b is more than or equal to 0.01 and less than or equal to 0.1 mol, and c is more than or equal to 0.01 and less than or equal to 0.05 mol.
A production method of an orange long afterglow luminescent material comprises the following steps:
a. providing yttrium oxide and Ti4+Compound of (2), containing Mg2+The compound, sulfur and sodium carbonate are used as raw materials, carbon is used as a reducing agent, and the mixture ratio of the raw materials is as follows: 0.9 to 0.99 mol of yttrium oxide and Ti4+0.01 to 0.1 mol of Mg2+0.01 to 0.05 mol, and sulfur is yttrium oxide and Ti4+Compound and Mg-containing compound2+30-40% of the total mass of the compounds, and sodium carbonate is yttrium oxide and contains Ti4+Compound and Mg-containing compound2+30-40% of the total mass of the compounds, and carbon is yttrium oxide and Ti4+Compound, Mg-containing2+1/4-1/2 of the sum of the mass of the compound, the sulfur and the sodium carbonate;
b. mixing the raw materials, and firing themixture for 3 to 6 hours under a reducing condition at the temperature of 200 to 500 ℃;
c. burning the product obtained in the step b for 1-3 hours at 1100-1300 ℃ under a reducing condition;
d. soaking the product obtained in the step c in hot water at the temperature of 75-85 ℃ for 2-3 hours, and then cleaning with hot water;
e. and d, drying the product obtained in the step d.
Said Ti-containing4+The compound of (b) is sodium titanate.
Said Mg-containing2+The compound of (2) is magnesium oxide.
The present invention relates to an orange-yellow long-afterglow luminescent material which uses yttrium oxysulfide as matrix, tetravalent titanium ion as activating agent, divalent magnesium ion as additive ion and sodium carbonate as cosolvent. Because the raw material does not contain rare earth ion thulium with higher price and replaces tetravalent titanium ion with lower price, the raw material cost of the product is lower; compared with the prior art, the high-temperature firing time is shortened by 2-3 hours, a large amount of electric energy is saved, and the manufacturing cost of the product is reduced; the product is soaked in hot water, so that hydrochloric acid is saved, and meanwhile, hydrogen sulfide gas harmful to the environment and human bodies is not generated, and the product is beneficial to environmental protection and human health.
The specific implementation mode is as follows:
example 1:
a. the raw materials were first weighed. Taking yttrium oxide (Y)2O3)203.4 g (0.9 mol), titanium dioxide 8 g (0.1 mol), magnesium oxide 0.4 g (Mg)2+0.01 mole), sulfur is 63.54 grams of the sum of the weight of yttrium oxide, titanium dioxide and magnesium oxide, and sodium carbonate is 63.54 grams of the sum of the weight of yttrium oxide, titanium dioxide and magnesium oxide. Carbon is about 1/2 of the sum of the mass of yttrium oxide, titanium dioxide, magnesium oxide, sulfur and sodium carbonate, and is about 169.44 g;
b. mixing the weighed raw materials, putting the raw materials into a crucible, placing 169.44 g of carbon rods around the crucible, and firing the carbon rods at the temperature of 200 ℃ for 3 hours;
c. then burning for 1 hour at 1100 ℃;
d. c, soaking the product obtained in the step c in 75 hot water for 2 hours, and then cleaning with hot water;
e. and d, drying the product obtained in the step d.
The reaction mechanism is as follows:
the light-emitting principle is as follows:
when the irradiation of visible light or ultraviolet ray is met, the energy is absorbed by magnesium ions firstly and transferred to titanium ions for storage, and when the irradiation is stopped, the stored energy is discharged outwards by the titanium ions, and the process of releasing the energy is the process of releasing light.
Example 2:
a. the raw materials were first weighed. Taking yttrium oxide (Y)2O3)223.74 g (0.99 mol), titanium dioxide 8 g (0.1 mol), magnesium oxide 2 g (Mg)2+0.05 mole), sulfur is 40% of the sum of the masses of yttrium oxide, titanium dioxide and magnesium oxide, i.e. 93.5 g, and sodium carbonate is 35% of the sum of the masses of yttrium oxide, titanium dioxide and magnesium oxide, i.e. 81.8 g. Carbon is about 1/4 of the sum of the mass of yttrium oxide, titanium dioxide, magnesium oxide, sulfur and sodium carbonate, and is about 102.26 g;
b. mixing the weighed raw materials, putting the raw materials into a crucible, placing a carbon rod around the crucible, and firing the mixture for 6 hours at the temperature of 500 ℃;
c. then, burning for 3 hours at 1300 ℃;
d. c, soaking the product obtained in the step c in hot water at 85 ℃ for 3 hours, and then cleaning with hot water;
e. and d, drying the product obtained in the step d.
The reaction mechanism and the light emitting principle are the same as those of example 1.
Example 3:
a. the raw materials were first weighed. 203.4 g (0.9 mol) of yttrium oxide and 1.42 g (0.01 mol) of sodium titanate are takenEr), basic magnesium carbonate of the formula Mg (OH)2·4MgCO3·5H2O0.968 g (Mg)2+0.01 mole), sulfur is 40% of the sum of the masses of yttrium oxide, sodium titanate and basic magnesium carbonate, i.e. 82.3 grams, and sodium carbonate is 40% of the sum of the masses of yttrium oxide, sodium titanate and basic magnesium carbonate, likewise 82.3 grams. The total mass of carbon yttrium oxide, sodium titanate, basic magnesium carbonate, sulfur and sodium carbonate is about 1/3, about 123.46G;
b. mixing the weighed raw materials, putting the raw materials into a crucible, placing 169.44 g of carbon rods around the crucible, and firing the carbon rods at the temperature of 400 ℃ for 5 hours;
c. then, the mixture is burned for 2.5 hours at the temperature of 1250 ℃;
d. c, soaking the product obtained in the step c in hot water at the temperature of 80 ℃ for 2.5 hours, and then cleaning with the hot water;
e. and d, drying the product obtained in the step d.
The reaction mechanism and the light emitting principle are the same as those of examples 1 and 2.
Claims (4)
1. An orange-yellow long afterglow luminescent material is characterized by comprising the following chemical components: aY2O2S：bTi4+，cMg2+Wherein a is more than or equal to 0.9 and less than or equal to 0.99 mol, b is more than or equal to 0.01 and less than or equal to 0.1 mol, and c is more than or equal to 0.01 and less than or equal to 0.05 mol.
2. The production process of orange-yellow long afterglow luminescent material as set forth in claim 1 includes the following steps:
a. providing yttrium oxide and Ti4+Compound of (2), containing Mg2+The compound, sulfur and sodium carbonate are used as raw materials, carbon is used as a reducing agent, and the mixture ratio of the raw materials is as follows: 0.9 to 0.99 mol of yttrium oxide and Ti4+0.01 to 0.1 mol of Mg2+0.01 to 0.05 mol, and sulfur is yttrium oxide and Ti4+Compound and Mg-containing compound2+30-40% of the total mass of the compounds, and sodium carbonate is yttrium oxide and contains Ti4+Compound and Mg-containing compound2+30-40% of the total mass of the compounds, and carbon is yttrium oxide and Ti4+Compound (I)Containing Mg2+1/4-1/2 of the sum of the mass of the compound, the sulfur and the sodium carbonate;
b. mixing the raw materials, and firing the mixture for 3 to 6 hours under a reducing condition at the temperature of 200 to 500 ℃;
c. burning the product obtained in the step b for 1-3 hours at 1100-1300 ℃ under a reducing condition;
d. soaking the product obtained in the step c in hot water at the temperature of 75-85 ℃ for 2-3 hours, and then cleaning with hot water;
e. and d, drying the product obtained in the step d.
3. The production method of the orange-yellow long-afterglow luminescent material as claimed in claim 2, wherein: said Ti-containing4+The compound of (b) is sodium titanate.
4. The production method of the orange-yellow long-afterglow luminescent material as claimed in claim 2 or 3, wherein: said Mg-containing2+The compound of (2) is magnesium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410020722 CN1266250C (en) | 2004-06-09 | 2004-06-09 | Orange long persistence fluorescent material and its production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410020722 CN1266250C (en) | 2004-06-09 | 2004-06-09 | Orange long persistence fluorescent material and its production |
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| CN1583950A CN1583950A (en) | 2005-02-23 |
| CN1266250C true CN1266250C (en) | 2006-07-26 |
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| CN 200410020722 Expired - Fee Related CN1266250C (en) | 2004-06-09 | 2004-06-09 | Orange long persistence fluorescent material and its production |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007145167A1 (en) * | 2006-06-12 | 2007-12-21 | Nemoto & Co., Ltd. | Phosphorescent/fluorescent material |
| CN100575452C (en) * | 2007-09-07 | 2009-12-30 | 中国科学院长春光学精密机械与物理研究所 | Orange-yellow long persistence phosphor and preparation method thereof |
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