CN1324910A - Long persistence phosphor of alkali earth aluminate for SiO2 glass painting and its prepn. method thereof - Google Patents
Long persistence phosphor of alkali earth aluminate for SiO2 glass painting and its prepn. method thereof Download PDFInfo
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Abstract
The present invention discloses an alkaline earth aluminate long-afterglow phosphor powder with SiO2 glass coating layer and its preparation method. This invented preparation method includes the following steps: hydrolyzing silicate in an aqueous solution containing cosolvent and catalyst to obtain an uniform transparent solution, mixing the above-mentioned alkaline earth aluminate long-afterglow phosphor powder and the above-mentioned obtained solutino according to a certain proportion, filtering, drying and heating so as to obtain the invented alkaline earth aluminate long-afterglow phosphor powder with SiO2 glass coating layer. It not only can raise water-proofing and heat-resisting properties, but also does not affect its luminous performance, and its preparation process is simple and easy to implement industrial production.
Description
The invention relates to an alkaline earth aluminate long afterglow fluorescent powder and a preparation method thereof.
With the high development of science and technology, the long afterglow photoluminescent energy storage material attracts attention, and has practical application in word panel display of aeronautical instruments and automobile instruments, paint, enamel, cement, industrial art and the like. Particularly, when the luminescent coating is used as road illumination, building signs and fire signs, the problem of power failure caused by sudden accidents such as earthquakes, fires and the like can be solved, so that the lives of people are saved.
Earlier long persistence phosphors were sulfide phosphors including CuS: Bi, CaSrS: Bi, ZnS: Cu, ZnCdS: Cu, etc., which were the first generation of long persistence phosphors with practical application significance. However, the material is unstable chemically, shows poor light resistance, is decomposed under certain humidity and ultraviolet radiation, turns black in color, and causes reduced brightness, thereby making it unsuitable for outdoor use and direct exposure to sunlight. The continuous luminescence time of ZnS: Cu is only dozens of minutes, and a small amount of radioactive substances such as Co, Pm and the like are added for the longer luminescence time and higher brightness. Since radioactive substances are harmful to human bodies and pollute the environment, their application is limited.
Unlike this sulfide light-emitting material, SrAl was found in Palilla (Palilla F C, This journal,1968,115,642) in the 60' s2O4:Eu2+The light emission process of (a) first undergoes a rapid decay process, and then in the lower intensity light emission range, there is a longer duration of light emission. This finding has led the alkaline earth aluminate long persistence luminescent materials to a new stage.
In recent years, SrAl is treated2O4:Eu2+The system development research focuses on partial replacement of Sr and Al with other components, and addition of a second activator other than Eu, such as Dy, Nd, etc., with the hope of achieving improvement in luminance and prolongation of afterglow time by introducing trace elements to form appropriate impurity levels. Chinese patent CN1126746A proposes O.Al with the general formula (A, Be)2O3The long-afterglow fluorescent powder of alkaline earth aluminate (A is single ion or combination of alkaline earth metal ions, Be is single ion or combination of Ce, Tb, Eu and Dy) has afterglow lasting for over 12 hr. It is found in Chinese patent CN1193651A that when the general formula is satisfied, the formula is (Sr)0.9995-0.998Eu0.0005-0.002)Al2O4Or (Sr)0.9995-0.998Eu0.0005-0.002O.n(All-abBbDy)O3(a =0.0005-0.002, b =0.001-0.35, n =1-8), and calcining at 1250-Glow time of more than 40 hoursThen (c) is performed. In JP8-73845, JP8-151573 and JP9-272867, alkaline earth aluminates are used as the base, and other components are added to further improve the luminous brightness and prolong the afterglow time.
Because of the safety, high brightness and long afterglow time of the alkaline earth aluminate long afterglow fluorescent powder, the fluorescent powder can be used for luminous printing ink, luminous paint, luminous enamel and the like, and is an excellent 'green light source'. However, they are a component of inks or paints and the like, and also have to satisfy the requirements of moisture resistance, heat resistance and weather resistance of luminescent articles. However, the most important disadvantage of the alkaline earth aluminate long afterglow phosphor is that the phosphor is extremely unstable to water and is easily hydrolyzed in aqueous solution, and even moisture in the air can greatly reduce the luminous brightness and afterglow time of the phosphor. For this reason, great efforts have been made to improve their water resistance and heat resistance. It was found in JP8-151574 that P is added to alkaline earth aluminates2O5In this case, water resistance and heat resistance can be improved. When P is present2O5When the molecular fraction of the light-emitting material is 0.002-0.04, the light-emitting brightness after being heated at 600 ℃ is 85% of the original brightness, and the brightness after being soaked for 72 hours is 48.5% of the original brightness. Without the addition of P2O5The luminance after heating at 600 ℃ was 20% of the original luminance, and the luminance after 72 hours of immersion was 0. Despite the addition of P2O5So that the heat resistance and the water resistance of the alkaline earth aluminate long afterglow phosphor are improved, but the use requirement can not be met.
In JP9-316443, basic specialty Chemicals of Japan, Inc. passed SiO2Surface treatment is carried out to improve the water resistance of the alkaline earth aluminate long afterglow fluorescent powder. The results show that when SiO is contained2When the concentration (wt%) of the treatment liquid is 7.5%, the pH value of the alkaline earth aluminate long afterglow fluorescent powder is kept unchanged after the alkaline earth aluminate long afterglow fluorescent powder is immersed in the water for 500 hours, and the material after surface treatment can be used for water-based ink or paint. However, in this patent opaque SiO is used2The colloidal emulsion is used as surface coating agent, and has improved water resistance and improved light-emitting brightness due to SiO on the surface2The crystalline particles are masked and reduced.
Chinese patent CN1241612A proposes that sodium silicate or potassium silicate is used as raw material in luminescent material matrixCoating a layer of sodium silicate or potassium silicate on the substrate, and calcining at high temperature to leave a layer of SiO outside the substrate2Crystalline, apparently SiO on said substrate2The crystals are discontinuous and there is also SiO present on the surface which is responsible for the brightness of the luminescence2The particles obscure the reduced defects.
One of the purposes of the invention is to disclose a method for preparing a silicon dioxide film with SiO on the surface2The long-afterglow alkaline earth aluminate fluorescent powder with glass coating is used to overcome the defects of poor heat resistance and water resistance and SiO-based luminous brightness in the prior art2Reduced defects masked by crystalline particles;
the second purpose of the invention is to provide a preparation method of the alkaline earth aluminate long afterglow fluorescent powder.
The idea of the invention is that:
the invention coats SiO on the surface of the prior alkaline earth aluminate long afterglow phosphor2A layer of molten glass fromTo form a surface with SiO2The alkaline earth aluminate long-afterglow fluorescent powder with the fused glass structure coating can improve the water resistance and the heat resistance of the alkaline earth aluminate long-afterglow fluorescent powder, and simultaneously does not influence the luminescence property of the material.
The technical scheme for realizing the purpose of the invention is as follows:
said surface of the invention has SiO2The glass-coated alkaline earth aluminate long-afterglowfluorescent powder comprises a substrate and SiO2A molten glass structural coating, said matrix being an alkaline earth aluminate having the formula:
MAl2O4:Eu.Dy
wherein M represents Mg, Ca, Sr or Ba, the preparation of the alkaline earth aluminate is a prior art and is completely described in Chinese patent CN1053807, CN1126746 and Japanese patent JP9-272867, and the description of the invention is not repeated.
Said SiO2The structural coating of the molten glass is SiO2The polymer of (1), having the formula:
wherein: n is the degree of polymerization, and n =5 ~ 20.
The thickness of the coating is SiO2In an amount of 0.1 to 25 wt.%, such as SiO2The amount of less than 0.1 wt%, a continuous film cannot be formed on the surface of the base body, so that the surface of the base body is exposed to the outside, affecting the water resistance and heat resistance thereof; when the amount of the coating is too large, the effective component of the luminescent material is reduced, and the luminous intensity per unit substrate is lowered. Preferred coating thicknesses are therefore SiO2The amount of (B) is 3-16 wt%.
Said SiO2The structural coating of the molten glass is a continuous SiO2A glass body having a structure of SiO2Completely different structures and properties of crystals, SiO2The crystals are a long range ordered structure, and the devitrified particles are opaque to light scattering in the coating. The SiO of the present invention2The molten glass structure is a short-range ordered structure when the SiO is continuous2When the glass body is coated on a substrate, the glass body has continuous and high transmittance in ultraviolet light-visible light-infrared light, so when the SiO is coated on the substrate2When the fused glass structure is coated outside the matrix of the luminescent material, the luminous intensity of the luminescent material is not influenced.
The surface has SiO2The preparation of the alkaline earth aluminate long afterglow fluorescent powder of the fused glass structure coating comprises the following steps:
(1) the structural formula is Si (OR)4The silicate ester is hydrolyzed in an aqueous solution containing a cosolvent and a catalyst to obtain a uniform and transparent solution;
wherein R is C1～C4Alkyl groups of (a);
H2O/Si(OR)41.0-15.0;
cosolvent/Si (OR)4In a molar ratio of from 10 to 60, preferably from 30 to 40;
the dosage of the catalyst is as follows: h+/Si(OR)4The molar ratio of (A) to (B) is 0.01 to 0.08, and the reaction time is 15 to 60 minutes.
Preferred is C1～C4The silicate of (A) is ethyl orthosilicate or butyl orthosilicate and a mixture thereof;
the cosolvent is C1～C3Preferably ethanol;
the catalyst is inorganic acid and C1～C4Organic acids of (1), including H2SO4、HCl、HNO3Or CH3One kind of COOH.
The reaction formula of the hydrolysis reaction is as follows:
in the formula: r is C1～C4N = 5-20.
As a result of the hydrolysis-condensation reaction, the structure changes from weak to higher cross-links. During heating, with further evaporation of water and alcohol and decomposition of the organic matter, it undergoes condensation to polymerization, the structure gradually densifying and finally transforming into the corresponding SiO2The molten glass also tends to devitrify during the melting. Thus, the corresponding SiO is to be obtained2The structure of the molten glass, the control of hydrolysis and heating conditions are very important.
Silicates are often stable to water because they are immiscible and hydrolysis can only be carried out by adding a co-solvent such as ethanol or the like to water and silicate to bring them into solution. General cosolvent to silicate molar ratio C2H5OH/Si(OR)4The content is controlled to be 10-60, preferably 30-40. With the reduction of the amount of the cosolvent, the surface coating of the alkaline earth aluminate particles is changed from uniform film forming to partial shrinkage and finally cracking without film forming, the surface part of the particles is still exposed, and the water resistance and the heat resistance are reduced. And co-solvent/Si (OR)4When the amount is more than 60, the bonding strength between the coating film and the surface of the alkaline earth aluminate is weakened, and the water resistance and heat resistance are deteriorated.
During the hydrolysis-condensation reaction of the silicon alcoholate, a suitable amount of water is necessary. When H is present2O/Si(OR)4When the molar ratio is less than 1, the solution viscosity increases, the coating thickness increases, and the pH of the coating composition is adjusted to alkaliThe surface of the aluminate long afterglow light accumulating powder has poor wettability, and the coating is easy to peel off. When H is present2O/Si(OR)4A molar ratio of more than 15 leads to SiO2Formation of spherical polymers, the presence of coarsened spherical particles in the coating, and the shadowThe transparency of the coating is affected, so that the relative luminous brightness of the coated alkaline earth aluminate long-afterglow fluorescent powder is reduced.
(2) Aging the solution at 40-60 deg.C for 12-72 hr, mixing the said long afterglow fluorescent powder with the aged solution, filtering, drying, and heating at 300-350 deg.C to obtain the product with SiO2Glass coating alkaline earth aluminate long afterglow fluorescent powder.
Aging of the hydrolyzed solution of tetraethylorthosilicate facilitates the formation of chain polymers. When the aging time is less than 12 hours, the solution viscosity is small, namely the polymerization degree is small, and a uniform and continuous film cannot be formed on the surface of the alkaline earth aluminate long afterglow light storage powder. When the amount is more than 72 hours, the viscosity increases, and the film formed on the surface of the alkaline earth aluminate long afterglow light accumulating powder is liable to crack, resulting in deterioration of water resistance and temperature resistance. The condensation reaction is facilitated by increasing the temperature, which is generally between 40 and 60 ℃, and the solvent is volatile at too high a temperature.
The material of the invention can improve the water resistance and heat resistance of the material and simultaneously keep higher relative brightness.
The powder obtained was tested using the following method:
the powder was immersed inwater, the pH of the aqueous solution was measured, and then filtered and dried to measure the relative light emission luminance. And heating at 500-900 deg.C for 30 min, and measuring relative brightness.
The results show that: the pH value of the solution is 6.5-7.5 after the solution is soaked in the aqueous solution for more than 1000 hours, and the relative light-emitting brightness is more than 90%. The relative light-emitting luminance after the heat treatment at 900 ℃ was 80%.
FIG. 1 shows the pH change of strontium aluminate long afterglow phosphor treated by surface coating and not treated by surface coating when immersed in water at different times.
Fig. 2 shows the relative brightness change of the strontium aluminate long afterglow phosphor treated by the surface coating and the strontium aluminate long afterglow phosphor not treated by the surface coating when the strontium aluminate long afterglow phosphor is immersed in water at different times.
Fig. 3 shows the relative brightness of the strontium aluminate long afterglow phosphor treated by the surface coating and the strontium aluminate long afterglow phosphor not treated by the surface coating after being heated at 500-900 ℃.
FIG. 4 shows the pH change of the calcium aluminate long-afterglow phosphor treated by surface coating and the calcium aluminate long-afterglow phosphor not treated by surface coating at different times when the phosphor is immersed in water.
FIG. 5 is a graph showing the relative brightness change of a surface-coated long-afterglow phosphor and a non-surface-coated calcium aluminate phosphor immersed in water at different times.
FIG. 6 shows the relative brightness of the calcium aluminate long afterglow phosphor treated with surface coating and the calcium aluminate long afterglow phosphor not treated with surface coating after heating at 500 deg.C-900 deg.C.
In fig. 1, curves 1 and 2 are the pH values of the strontium aluminate long afterglow phosphor powder without and after surface coating treatment after being soaked in water for different times, respectively. As can be seen from FIG. 1, the strontium aluminate long afterglow phosphor without surface coating treatment is very unstable in water and very fast in hydrolysis, and the pH value is more than 14 within 1 hour, while the treated strontium aluminate long afterglow phosphor is stable to water and not hydrolyzed in water, and the pH value is kept constant between 6.5 and 7.5.
In fig. 2, curves 3 and 4 are the relative luminance after the strontium aluminate long afterglow phosphor without and after surface coating treatment is soaked in water for different times, respectively. As can be seen from FIG. 2, the hydrolysis of the strontium aluminate long afterglow phosphor powder without surface coating treatment in water results in crystal structure collapse, and the relative luminous brightness decreases rapidly with the increase of the soaking time, while the surface coating of the strontium aluminate long afterglow phosphor powder with surface coating treatment is water-resistant, so that the luminous brightness can still be maintained at 90% or more even after soaking for 1000 hours.
In FIG. 3, curves 5 and 6 are the non-surface coating treatmentsAnd the relative luminous brightness of the strontium aluminate long afterglow phosphor treated by the surface coating after being heated for 0.5 hour at the temperature of 500-900 ℃. As can be seen from FIG. 3, after the surface coating treatment, the surface had dense SiO2A glass film for preventingoxygen from diffusing into the crystal lattice and making Eu in the crystal lattice2+A considerable amount of Eu is maintained even at a relatively high temperature2+Eu at high temperature without surface coating treatment while keeping 80% relative brightness2+Oxidized to Eu3+The relative light emission luminance was reduced to 0% of the original luminance.
In FIG. 4, curves 7 and 8 are the pH values of the calcium aluminate long afterglow phosphors without and after surface coating treatment, respectively, after soaking in water for different periods of time. As can be seen from FIG. 4, the calcium aluminate long afterglow phosphor without surface coating treatment hydrolyzes very fast in water, while the treated phosphor is stable to water and the pH value is maintained at a constant value of 6.5 to 8.6.
In FIG. 5, curves 9 and 10 are the relative luminance after soaking the calcium aluminate long afterglow phosphors without and after surface coating treatment in water for different periods of time, respectively. As can be seen from FIG. 5, the strontium aluminate long afterglow phosphor without surface coating treatment has a relative luminance of 0% after soaking for 1 hour, while the strontium aluminate long afterglow phosphor treated with surface coating has a relative luminance of more than 80% with time.
In FIG. 6, curves 11 and 12 are the relative luminance of the calcium aluminate long afterglow phosphors without and after surface coating treatment after heating at 500-900 deg.C for 0.5 hr. As can be seen from fig. 6, the heat resistance was greatly improved after the surface coating treatment, and the relative luminance remained 80% even after the high temperature treatment at 900 ℃, whereas the luminance remained 0% without the surface coating treatment.
In conclusion, the invention can obviously improve the water resistance and the heat resistance of the alkaline earth aluminate long afterglow fluorescent powder, simultaneously keeps higher relative brightness, has simple process and is easy for industrialized production.
The present invention will be further illustrated by the following examples, which, however, do not limit the scope of the present invention.
Example 1
Mixing 10g of ethyl orthosilicate and 5g of H2O、76gC2H5OH and 0.2g HCl are mixed, ethyl orthosilicate is added under the condition of stirring, stirring is continued for 15 minutes to form a uniform transparent solution, and the solution is aged for 72 hours at the temperature of 40 ℃. Taking 46g of strontium aluminate long afterglow phosphor (emission main peak 520nm, particle size d)5035 μ) was mixed with the above clear solution and stirred for 15 minutes, filtered, and naturally dried. Then heat-treating at 350 deg.C for 30 min to obtain SiO2Coating amount of 5% with SiO2The glass coating is alkaline earth strontium aluminate long afterglow phosphor. They were then soaked in water and heated at 500-900 ℃ for 30 minutes, and their pH and relative brightness were observed. As shown in fig. 1, 2 and 3, the results show that: the pH value of the solution is 6.5 after soaking in the aqueous solution for more than 1000 hours, and the relative luminous brightness is 100 percent. The relative light-emitting luminance after the heat treatment at 900 ℃ was 85%.
Example 2
10g of tetraethoxysilane, 7gH2O、76g C2H5OH、0.1gCH3COOH, adding tetraethoxysilane under the condition of stirring, continuing stirring for 15 minutes to obtain a uniform transparent solution, and aging for 48 hours at 50 ℃. 30g of commercial calcium aluminate long afterglow phosphor (emission main peak 420nm, particle size d50 is 40 mu) is mixed with the transparent solution and stirred for 15 minutes, filtered, naturally dried and then thermally treated at 320 ℃ for 30 minutes to obtain SiO2Coating amount of 10% with SiO2The alkaline earth calcium aluminate long afterglow phosphor powder of glass coating. They were then soaked in water and heated at 500-900 ℃ for 30 minutes, and their pH and relative brightness were observed. As shown in fig. 4, 5 and 6, the results are shown below: the pH value is 7.0 when the LED is soaked in the aqueous solution for more than 1000 hours, and the relative luminous brightness is 100 percent. The relative light-emitting luminance after the heat treatment at 900 ℃ was 82%.
Example 3
The same procedure as in example 1 was followed at 0.1g H2SO4Instead of HCl, the results are as follows: the pH value of the solution is 6.5 after soaking in the aqueous solution for more than 1000 hours, and the relative luminous brightness is 100 percent. The relative light-emitting luminance after the heat treatment at 900 ℃ was 85%.
Example 4
The same procedure as in example 1 was followed, using 15g of n-butyl orthosilicate instead of ethyl orthosilicate, to obtain a mixture
The following fruits were obtained: the pH value is 6.5 when the LED is soaked in the aqueous solution for more than 1000 hours, and the relative luminous brightness is more than 98.5 percent. The relative light-emitting luminance after the heat treatment at 900 ℃ was 80%.
Example 5
In the same manner as in example 1, 1.5g of ethyl orthosilicate was used to obtain SiO2Coating amount of 0.75% with SiO2The result of the glass coating alkaline earth strontium aluminate longafterglow phosphor is as follows: the pH value is 7.0 when the LED is soaked in the aqueous solution for more than 1000 hours, and the relative luminous brightness is more than 98 percent. The relative light-emitting luminance after the heat treatment at 900 ℃ was 80%.
Example 6
The same procedure as in example 1 was used, with 2.5g of a mixture of butyl orthosilicate and ethyl orthosilicate (1: 1, weight ratio) being substituted for ethyl orthosilicate, the results being as follows: the pH value is 7.5 when the LED is soaked in the aqueous solution for more than 1000 hours, and the relative luminous brightness is more than 98 percent. The relative light-emitting luminance after the heat treatment at 900 ℃ was 82%.
Claims (10)
1. Has SiO2The long afterglow fluorescent powder of alkali earth aluminate with glass coating includes one base body and one coating layer, and the base body is alkali earth aluminate with the chemical formula:
MAl2O4:Eu.Dy
wherein M represents Mg, Ca, Sr or Ba, characterized in that the coating is SiO2A molten glass structural coating having the formula:
wherein: n = 5-20, and the thickness of the coating is SiO2The amount of (B) is 0.1 to 25 wt%.
2. The phosphor of claim 1, wherein the coating thickness is SiO2The amount of (B) is 3-16 wt%.
3. The method of preparing the phosphor of claim 1, comprising the steps of:
(1) the structural formula is Si (OR)4The silicate ester is hydrolyzed in an aqueous solution containing a cosolvent and a catalyst to obtain a uniform and transparent solution;
wherein R is C1～C4Alkyl groups of (a);
H2O/Si(OR)4the molar ratio of (A) is 1.0-15.0;
cosolvent/Si (OR)4The molar ratio of (A) is 10-60;
the dosage of the catalyst is as follows: h+/Si(OR)4The molar ratio of (A) to (B) is 0.01-0.08;
the cosolvent is C1～C3The fatty alcohol of (a);
the catalyst is inorganic acid and C1～C4An organic acid of (4);
(2) aging the solution, mixing the alkaline earth aluminate long afterglow light accumulating powder and the aged solution in certain proportion, filtering, drying and heating to obtain SiO-bearing powder2Glass coating alkaline earth aluminate long afterglow fluorescent powder.
4. The method of claim 3 wherein the silicate is ethyl or butyl orthosilicate and mixtures thereof.
5. The method of claim 3 or 4, wherein the co-solvent is ethanol.
6. As claimed in claim3 or the preparation method of the fluorescent powder, characterized in that the catalyst comprises H2SO4、HCl、HNO3Or CH3One kind of COOH.
7. The method of claim 3, wherein the cosolvent/Si (OR)4Is 30 to 40.
8. The method of claim3, wherein the solution is aged at 40-60 ℃ for 12-72 hours.
9. The method of claim 3, wherein the heating is carried out at 300-350 ℃.
10. Has SiO2The long afterglow fluorescent powder of alkali earth aluminate with glass coating includes one base body and one coating layer, and the base body is alkali earth aluminate with the chemical formula:
MAl2O4:Eu.Dy
wherein M represents Mg, Ca, Sr or Ba, characterized in that the coating is SiO2A molten glass structural coating having the formula:
wherein: n = 5-20, and the thickness of the coating is SiO2The amount of (B) is 0.1-25 wt%;
the phosphor is prepared by:
(1) the structural formula is Si (OR)4The silicate ester is hydrolyzed in an aqueous solution containing a cosolvent and a catalyst to obtain a uniform and transparent solution;
wherein R is C1～C4Alkyl groups of (a);
H2O/Si(OR)41.0-15.0;
cosolvent/Si (OR)4The molar ratio of (A) is 10-60;
the dosage of the catalyst is as follows: h+/Si(OR)4The molar ratio of (A) to (B) is 0.01-0.08;
the cosolvent is C1～C3The fatty alcohol of (a);
the catalyst is H2SO4、HCl、HNO3Or CH3One of COOH;
(2) aging the solution at 40-60 ℃ for 12-72 hours, mixing the alkaline earth aluminate long afterglow fluorescent powder and the aged solution in proportion, filtering, drying, and heating at 300-350 ℃ to obtain the product with SiO2Glass coating alkaline earth aluminate long afterglow fluorescent powder.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003089382A1 (en) * | 2002-04-16 | 2003-10-30 | Katco Corporation | Luminous cementitious composition and methods of making and using the same |
| CN1298807C (en) * | 2002-11-01 | 2007-02-07 | 中国科学院大连化学物理研究所 | Functional nano-rare earth fluorescent micro particle and its preparation and application |
| CN101665690B (en) * | 2009-09-23 | 2012-07-25 | 东南大学 | Preparation method of waterproof fluorescent powder |
| CN106433612A (en) * | 2016-09-19 | 2017-02-22 | 绍兴文理学院 | Preparation method of waterproof fluorescent powder |
| CN111234806A (en) * | 2019-12-12 | 2020-06-05 | 集美大学 | Aluminate long afterglow material, coating paint and preparation method thereof |
| CN114805995A (en) * | 2022-04-27 | 2022-07-29 | 安踏（中国）有限公司 | High-luminosity long-afterglow luminous EVA (ethylene-vinyl acetate copolymer) foamed sole as well as preparation method and application thereof |
-
2001
- 2001-06-29 CN CNB011132000A patent/CN1159408C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003089382A1 (en) * | 2002-04-16 | 2003-10-30 | Katco Corporation | Luminous cementitious composition and methods of making and using the same |
| CN1298807C (en) * | 2002-11-01 | 2007-02-07 | 中国科学院大连化学物理研究所 | Functional nano-rare earth fluorescent micro particle and its preparation and application |
| CN101665690B (en) * | 2009-09-23 | 2012-07-25 | 东南大学 | Preparation method of waterproof fluorescent powder |
| CN106433612A (en) * | 2016-09-19 | 2017-02-22 | 绍兴文理学院 | Preparation method of waterproof fluorescent powder |
| CN106433612B (en) * | 2016-09-19 | 2021-03-16 | 绍兴市梓昂新材料有限公司 | Preparation method of waterproof fluorescent powder |
| CN111234806A (en) * | 2019-12-12 | 2020-06-05 | 集美大学 | Aluminate long afterglow material, coating paint and preparation method thereof |
| CN114805995A (en) * | 2022-04-27 | 2022-07-29 | 安踏（中国）有限公司 | High-luminosity long-afterglow luminous EVA (ethylene-vinyl acetate copolymer) foamed sole as well as preparation method and application thereof |
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| CN1159408C (en) | 2004-07-28 |
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