# US 2009/0014684 A1 · Long afterglow luminescent material with compounded substrates and its preparation method

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- Number: US 2009/0014684 A1
- Document ID: US20090014684A1
- Status: Published application
- Kind: A1
- Application number: 11/993,574
- Filed: 2006-06-22
- Published: 2009-01-15
- Earliest claimed: 2005-07-01
- Assignees: Sichuan Sunfor Light Co., Ltd.
- Inventors: Ming Zhang; Li Zhang; Xiaolei Zhang; Qiang Zhang
- Web page: https://patentgrep.com/patent/US20090014684A1

## CPC

- C09K 11/7796: {with alkaline earth metals}
- C04B 35/447: based on phosphates {, e.g. hydroxyapatite}
- C09K 11/7778: {with alkaline earth metals}
- C04B 2235/3201: Alkali metal oxides or oxide-forming salts thereof
- C04B 2235/3206: Magnesium oxides or oxide-forming salts thereof
- C04B 2235/3208: Calcium oxide or oxide-forming salts thereof, e.g. lime
- C04B 2235/3213: Strontium oxides or oxide-forming salts thereof
- C04B 2235/3215: Barium oxides or oxide-forming salts thereof
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3224: Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/3227: Lanthanum oxide or oxide-forming salts thereof
- C04B 2235/3229: Cerium oxides or oxide-forming salts thereof
- C04B 2235/3262: Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B 2235/3284: Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
- C04B 2235/3409: Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
- C04B 2235/3418: Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
- C04B 2235/446: Sulfides, tellurides or selenides
- C04B 2235/9661: Colour
- C04B 2235/9669: Resistance against chemicals, e.g. against molten glass or molten salts
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE

## Abstract

The present invention provides a new ultra-long after-glow phosphorescent material and manufacturing method for the same. The said materials include a phosphor including aMS.bM3(PO4)2.cMSiO2.dMO.fAl2O3.xRO.yTR2O3.zMnO, where the M is Ca, Mg, Ba, Sr, Zn or combinations thereof, The R is Eu, Sm, Yb, Pr and Nd or combinations thereof; the TR is La, Y, Nd, Dy, Er, Tu, Ce, Ho or combinations thereof; and a, b, c, d, f x, y, z is the number of mol. The phosphorescent material has superior water resistance and temperature resistance.

## Claims

### Claim 1

An ultra-long after-glow phosphorescent material, comprising a phosphor depicted by the formula
ams.bM3(PO4)2.cMSiO3.dMO.fA12O3.xRO.yTR2O3.zMnO;
where M is at least one of Ca, Mg, Ba, Sr, Zn;
R is at least one of Eu, Sm, Yb, Pr and Nd;
TR is at least one of La, Y, Nd, Dy, Er, Tu, Ce, and Ho;
and each of a, b, c, d, f x, y, z is a number of moles, wherein:
0.01≦a≦8;
0.01≦b≦6;
0.01≦c≦2
0.01≦d≦7;
0.01≦f≦7;
0.0001≦x≦0.5;
0.0001≦y≦0.5; and
0.001≦z≦0.2.

### Claim 2 (depends on 1)

The ultra-long after-glow phosphorescent material as claimed in claim 1, wherein the said a, b, c, d, f x, y, z respectively are:
0.01≦z≦5;
0.01≦b≦1.5;
0.01≦c≦1;
0.01≦d≦5;
0.01≦f≦5;
0.0001≦x≦0.01;
0.001≦y≦0.01;
0.001≦z≦0.1;

### Claim 3 (depends on 1)

The ultra-long after-glow phosphorescent material as claimed in claim 1, wherein the said ultra-long after-glow phosphorescent material is:
0.05431SrS.0.027 Sr3(PO4)2.0.1997 SrSiO3.0.3915SrO.0.5013Al2O3.0.008EuO.0.0083Dy2O3.0.0021Ce2O3.0.0044MnO;
0.1SrS.0.0176Sr3(PO4)2.0.149 SrSiO3.0.3807SrO.0.3137Al2O3.0.0625EuO.0.00723Dy2O3.0.00152Ce2O3.0.00174MnO;
0.4375SrS.0.02817Sr3(PO4)2.0.0582 SrSiO3.0.3895SrO.0.3627Al2O3.0.0056EuO.0.0071Dy2O3.0.001513Ce2O3.0.00522MnO;
0.053SrS.0.0275Sr3(PO4)2.0.2 SrSiO3.0.233SrO.0.5735Al2O3.0.004EuO.0.00873Dy2O3.0.00217Ce2O3.0.00435MnO;
0.1625SrS.0.0176Sr3(PO4)2.0.1 SrSiO3.0.1625SrO.0.5264Al2O3.0.0051EuO.0.00723Dy2O3.0.00435Ce2O3.0.6MnO;
0.281SrS.0.0282Sr3(PO4)2.0.1167 SrSiO3.0.1235SrO.0.5784Al2O3.0.005317EuO.0.0071Dy2O3.0.1167Ce2O3.0.6MnO;
0.281CaS.0.0286Ca3(PO4)2.0.1167 CaSiO3.0.33CaO.0.5764Al2O3.0.00165PrO.0.0071Dy2O3.0.1157Ce2O3.0.6MnO;
0.281MgS.0.0282Mg3(PO4)2.0.1167 MgSiO3.0.4404MgO.0.5784Al2O3.0.00291NdO.0.0071Dy2O3.0.1167Ce2O3.0.60; or
0.281BaS.0.0282Ba3(PO4)2.0.1167BaSiO3.0.2235BaO.0.5784Al2O3.0.005317EuO.0.0071Tm2O3.0.1167Ce2O3.0.6MnO.

### Claim 4

A method for manufacturing an ultra-long after-glow phosphorescent material, the phosphorescent material comprising a phosphor depicted by
aMS.bM3(PO4)2.cMSiO3.dMO.fA12O3.xRO.yTR2O3.zMnO, where
M is at least one of Ca, Mg, Ba, Sr, Zn;
R is at least one of Eu, Sm, Yb, Pr, Nd;
TR is at least one of La, Y, Nd, Dy, Er, Tu, Ce, Ho;
and each of a, c, d, f x, y, z is a number of moles, wherein:
0.01≦a≦8;
0.01≦b≦6;
0.01≦c≦2;
0.01≦d≦7;
0.01≦f≦7;
0.0001≦x≦0.5;
0.0001≦y≦0.5;
0.001≦z≦0.2;
wherein the method comprises the following steps:
1) using oxides, carbonates, oxalates, nitrates or hydroxides of M as a raw material of M; sulfur as a raw material of S; phosphorus pentoxide (P2O5), ammonium dihydrogen phosphate (NH4H2PO4) as a raw material of phosphorus; silicon dioxide as a raw material of silicon; alumina, aluminum hydroxide as a raw material of alumina; Oxides of R as a raw material of RO; Oxides of elements corresponding to TR as a raw material of TR2O3;
provided that weight ratios of these raw materials satisfy the above relation of a, b, c, d, f, x, y, and z; and also using urea at a molar ratio of urea to M of 0.1-1:1 and LiCl at a molar ratio of LiCl to M of 0.0165-1:1;
2) Mixing the above raw materials thoroughly, filling NH3 or adding carbon granules into the mixture, and calcining at 1200-1450° C. for 1-4 h to provide the ultra-long after-glow phosphorescent material.

### Claim 5 (depends on 4)

The method as claimed in claim 4, wherein the said a, b, c, d, f, x, y, z respectively are:
0.01≦z≦5;
0.01≦b≦1.5;
0.01≦c≦1;
0.01≦d≦5;
0.01≦f≦5;
0.0001≦x≦0.0;
0.001≦y≦0.01;
0.001≦z≦0.1.

### Claim 6 (depends on 4)

The method as claimed in claim 4, wherein the said ultra-long after-glow phosphorescent material is
0.05431SrS.0.027 Sr3(PO4)2.0.1997 SrSiO3.0.3915SrO.0.5013Al2O3.0.008EuO.0.0083Dy2O3.0.0021Ce2O3.0.0044MnO;
0.1SrS.0.0176Sr3(PO4)2.0.149 SrSiO3.0.3807SrO.0.3137Al2O3.0.0625EuO.0.00723Dy2O3.0.00152Ce2O3.0.00174MnO;
0.4375SrS.0.02817Sr3(PO4)2.0.0582 SrSiO3.0.3895SrO.0.3627Al2O3.0.0056EuO.0.0071Dy2O3.0.001513Ce2O3.0.00522MnO;
0.053SrS.0.0275Sr3(PO4)2.0.2 SrSiO3.0.233SrO.0.5735Al2O3.0.004EuO.0.00873Dy2O3.0.00217Ce2O3.0.00435MnO;
0.1625SrS.0.0176Sr3(PO4)2.0.1 SrSiO3.0.1625SrO.0.5264Al2O3.0.0051EuO.0.00723Dy2O3.0.00435Ce2O3.0.6MnO;
0.281SrS.0.0282Sr3(PO4)2.0.1167 SrSiO3.0.1235SrO.0.5784Al2O3.0.005317EuO.0.0071Dy2O3.0.1167Ce2O3.0.6MnO;
0.281CaS.0.0286Ca3(PO4)2.0.1167 CaSiO3.0.33CaO.0.5764Al2O3.0.00165PrO.0.0071Dy2O3.0.1157Ce2O3.0.6MnO;
0.281MgS.0.0282Mg3(PO4)2.0.1167 MgSiO3.0.4404MgO.0.5784Al2O30.00291NdO.0.0071Dy2O3.0.1167Ce2O3.0.6MnO; or
0.281BaS.0.0282Ba3(PO4)2.0.1167 BaSiO3.0.2235BaO.0.5784Al2O3.0.005317EuO.0.0071Tm2O3.0.1167Ce2O3.0.6MnO.

### Claim 7 (depends on 4)

The method as claimed in claim 4, further comprising a step of comminuting the obtained ultra-long after-glow phosphorescent material by calcination and treating the material with ethyl orthosilicate or methyl silicone oil solution of 0.1-2% concentration (by weight).

### Claim 8 (depends on 7)

The method as claimed in claim 7, wherein the ultra-long after-glow phosphorescent material is comminuted to nanometer scale.

### Claim 9 (depends on 1)

An article, comprising the ultra-long after-glow phosphorescent material as claimed in claim 1.

### Claim 10 (depends on 9)

The article as claimed in claim 9, wherein the said article is ceramic and is prepared by calcining the said ultra-long after-glow phosphorescent material with ceramic raw materials together at 500-1000° C.

### Claim 11 (depends on 9)

The article as claimed in claim 9, wherein the said a, b, c, d, f, x, y, z respectively are:
0.01≦a≦5;
0.01≦b≦1.5;
0.01≦c≦1;
0.01≦d≦5;
0.01≦f≦5;
0.0001≦x≦0.01;
0.001≦y≦0.01;
0.001≦z≦0.1.

### Claim 12 (depends on 9)

The article as claimed in claim 9, wherein the said ultra-long after-glow phosphorescent material is:
0.05431SrS.0.027 Sr3(O4)2.0.1997 SrSiO3.0.3915SrO.0.5013Al2O3.0.008EuO.0.0083Dy2O3.0.0021Ce2O3.0.0044MnO;
0.1SrS.0.0176Sr3(PO4)2.0.149SrSiO3.0.3807SrO.0.3137Al2O3.0.0625EuO.0.00723Dy2O3.0.00152Ce2O3.0.00174MnO;
0.4375SrS.0.02817Sr3(PO4)2.0.0582SrSiO3.0.3895SrO.0.3627Al2O3.0.0056EuO.0.0071Dy2O3.0.001513Ce2O3.0.00522MnO;
0.053SrS.0.0275Sr3(PO4)2.0.2SrSiO3.0.233SrO.0.5735Al2O3.0.004EuO.0.00873Dy2O3.0.00217Ce2O3.0.00435MnO;
0.1625SrS.0.0176Sr3(PO4)2.0.1SrSiO3.0.1625SrO.0.5264Al2O3.0.0051EuO.0.00723Dy2O3.0.00435Ce2O3.0.6MnO;
0.281SrS.0.0282Sr3(PO4)2.0.1167SrSiO3.0.1235SrO.0.5784Al2O3.0.005317EuO.0.0071Dy2O3.0.1167Ce2O3.0.6MnO;
0.281CaS.0.0286Ca3(PO4)2.0.1167CaSiO3.0.33CaO.0.5764Al2O3.0.00165PrO.0.0071Dy2O3.0.1157Ce2O3.0.6MnO;
0.281MgS.0.0282Mg3(PO4)2.0.1167MgSiO3.0.4404MgO.0.5784Al2O3.0.00291NdO.0.0071Dy2O3.0.1167Ce2O3.0.6MnO; or
0.281BaS.0.0282Ba3(PO4)2. 0.1167BaSiO3.0.2235BaO.0.5784Al2O3.0.005317EuO.0.0071Tm2O3.0.1167Ce2O3.0.6MnO.