CN101186821A - Ca1-xSrZnMxFBr1-yIy:Rez'Cd0.05 optical storage luminescent material and preparation method thereof - Google Patents

Abstract

The invention belongs to luminous materials for optical storage, in particular relating to a luminous material for optical storage of Ca1-xSrZnMxFBr1-yIy: Rez, Cd0.05, which is employed to detect diagnostic images of X-ray of medical treatment and is coactivated by rare earth and cadmium ion which are coated on the surface of polymer with industrial nondestructive inspection. The invention also provides a process for preparing the luminous material for optical storage. The novel luminous material for optical storage of the invention is matched with an adjustable broad band of which the wavelength is between 650 nanometers and 1000 nanometers, and the adjustable broad band suits all semiconductor lasers in the wave band, wherein the semiconductor lasers are taken as driving light sources matched with the adjustable broad band, thereby greatly improving utilization convenience of a x-ray image plate which is produced by employing the sample to coat and increasing elastic range of choosing the matching driving light sources. In particular, the luminous property of the invention is further promoted by coating the surface via the polymer.

Description

Ca1-xSrZnMxFBr1-yIy: Rez, Cd0.05 light-storage luminescent material and its preparation method

【Technical field】

The invention belongs to light storage luminescent materials, in particular to Ca _1-x SrZnM _x FBr _1-y I _y : Re _z co-activated by rare earth and cadmium ions on the surface of a polymer that can be used to detect medical X-ray diagnostic images and industrial non-destructive testing , Cd _0.05 light-storage luminescent material and its preparation method.

【Background technique】

At present, BaFx:Re is an excellent light-storage luminescent material, and is widely used in medical X-ray diagnostic imaging and industrial non-destructive testing image detection. At present, Japanese Patent Application Laid-Open Specification 2001-011439 discloses doping monovalent metal ions in barium fluoride halide europium (BaFX:Eu, X is a halogen or a combination of halogens); Europium (BaFX: Eu, x is a halogen or a combination of halogens) is doped with divalent metal ions; Japanese Patent 2001-144128 discloses the use of barium europium fluoride halides (BaFx: Eu, X is a halogen or a combination of halogens) co-doped monovalent and tetravalent metal ions; U.S. Patent 6180949 also disclosed co-doped monovalent and divalent and trivalent or compounds of tetravalent metal ions. In the above-mentioned patent, the x-ray imaging plate made of the light storage luminescent material of the compound is used in conjunction with a matched laser suitable for a short wave band. Such as: yttrium aluminum garnet doped neodymium (Nd:YAG) laser, argon ion laser or helium neon laser. However, the excitation wavelength peak of this kind of optical storage luminescent material must be near the wavelength emitted by these lasers, otherwise, the image will be blurred, the gray scale is not rich, and the image cannot even be read. In addition, the relatively expensive and bulky defects of this type of laser are accompanied by people's higher and higher requirements for ease of use. People hope to replace the yttrium aluminum garnet used in the short-wave band with the existing cheap and compact semiconductor lasers. Neodymium-doped (Nd:YAG) lasers, argon-ion lasers, or helium-neon lasers. my country's patent publication No. CN1408814A reports a compound formed by doping trivalent and tetravalent metal ions in the synthesized rare earth ion-activated barium fluoride bromide iodide (BaFBrI:Re), and the matching excitation wavelength is 650 nm-700 nm , which simplifies the design of the readout system. However, for optical storage materials, improving optical storage efficiency, increasing excitation luminescence intensity, and adjusting the required excitation wavelength are important aspects of research, especially through surface treatment of optical storage materials to improve luminescence performance.

【Content of invention】

The object of the present invention is to overcome the deficiencies of the prior art, and provide an optical storage material with polymer surface coating, adjustable excitation wavelength, improved optical storage efficiency and a preparation method of the optical storage material. A cheap and compact semiconductor laser is used as the excitation light source, thereby improving the convenience of use and the luminous performance of the X-ray imaging plate made by coating the sample.

The technical solution adopted by the present invention to solve the above problems is to provide a Ca _1-x SrZnM _x FBr _1-y I _y : Re _z , Cd _0.05 light storage luminescent material, which is characterized in that the purity of the raw materials selected is Analytical grade, including CaCO ₃ , SrCO ₃ , ZnO, Cd0, NH ₄ F, NH ₄ Br, NH ₄ I, the source of rare earth ions (Re), is one of its oxides, halides, nitrates or sulfates One provided; the source of the doped trivalent metal ion M is provided by one of its oxides, halides or carbonates, the solvent is water or ethanol, and the surface coating material is methyl methacrylate Fat; its chemical expression is:

Ca _1-x SrZnM _x FBr _1-y I _y : Re _z , Cd _0.05

Wherein, M is an element in Al, In, Sc, Y;

Re is a rare earth ion, which is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy) , one of holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);

The value ranges of x, y, and z are: 0.0001<x≤0.6, 0.0001<y≤0.6; 0.0001<z≤1.

The present invention also provides a Ca _1-x SrZnM _x FBr _1-y I _y : Re _z , Cd _0.05 optical storage material preparation method, characterized in that the preparation process is:

1) Mix the raw materials according to the stoichiometric ratio, add a solvent to fully grind, and then dry;

2) Using solid-state reaction, burn the ground raw materials in a reducing atmosphere at a high temperature of 800-1400°C for 2-6 hours, and cool the burned samples to room temperature with the furnace temperature;

3) After grinding the sample, sieve it, wash it twice with a solvent, and dry the sample;

4) Mix the dried sample with a methyl methacrylate solution of 1/2 the sample mass, dry it at 90--160°C for 2 hours, grind the sample and sieve it, wash it twice with a solvent, and dry the sample You can paint the screen.

The above-mentioned drying method is a heating drying method; the drying temperature is preferably 0-160°C.

The above burning atmosphere is a reducing atmosphere, and the reducing atmosphere can be selected from one of the following: activated carbon powder, surrounded by graphite, nitrogen or a mixture of nitrogen and hydrogen.

The novel optical storage luminescent material of the present invention, Ca _1-x SrZnM _x FBr _1-y I _y : Re _z , Cd _0.05 matches an adjustable broadband between 650 nanometers and 1000 nanometers. There is little difference in the excitation luminance brightness of different wavelengths, and it is suitable for all semiconductor lasers in this band as its matching excitation light source. It is suitable for cheap and compact semiconductor lasers as its excitation light source, thereby greatly improving the convenience of use of the x-ray image plate made by coating the sample, and increasing the flexibility range of selecting a matching excitation light source. In particular, its luminescent performance is further improved by polymer surface coating.

【Detailed ways】

The purity of raw materials of the present invention is analytically pure, including CaCO ₃ , SrCO ₃ , ZnO, Cd0, NH ₄ F, NH ₄ Br, NH ₄ I, and the source of rare earth ions (Re), which are composed of oxides, halides, Nitrate, sulfate provided by one of them; the source of the mixed trivalent metal ion M is provided by one of its oxide, halide, carbonate, the solvent is water and ethanol, the surface coating The coating material is methyl methacrylate; its chemical expression is:

Ca _1-x SrZnM _x FBr _1-y I _y : Re _z , Cd _0.05

Wherein, M is an element in Al, In, Sc, Y;

Re is a rare earth ion, which is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy) , one of holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);

The value ranges of x, y, and z are: 0.0001<x≤0.6, 0.0001<y≤0.6; 0.0001<z≤1.

In the chemical expression of the optical storage material Ca _1-x SrZnM _x FBr _1-y I _y : Re _z , Cd _0.05 , the value of x can also be in the following range:

0.001<x≤0.1, 0.0001<y≤0.1, 0.0001<z≤0.1.

Optical storage materials can be expressed by the following chemical expressions:

(1) Ca _0.9 SrZnAl _0.1 FBr _0.9 I _0.1 :Eu _0.06 , Cd _0.05 ;

(2) Ca _0.5 SrZnY _0.5 FBr _0.7 I _0.3 : Pr _0.04 , Cd _0.05 .

In addition, the specific embodiment of the optical storage material can also be determined according to the data in the table:

m Re x y z 1 Al Eu 0.01 0.01 0.02 2 In Eu 0.001 0.001 0.1 3 Sc Eu 0.1 0.08 0.2 4 Y Eu 0.3 0.05 0.1 5 Al Pr 0.41 0.1 0.02

6 In Ce 0.05 0.4 0.03 7 Sc Dy 0.06 0.2 0.42 8 Y Er 0.08 0.5 0.4 9 Al Tb 0.09 0.2 0.3 10 In Ho 0.4 0.09 0.23 11 Sc Tm 0.1 0.07 0.04 12 Y Sm 0.5 0.09 0.2

The optical storage material of the present invention can be prepared according to the following embodiments:

Example 1

Taking Ca _0.9 SrZnAl _0.1 FBr _0.9 I _0.1 :Eu _0.06 , Cd _0.05 as an example, according to the stoichiometric ratio, CaCO ₃ , SrCO ₃ , ZnO, Cd0, NH ₄ F, NH ₄ Br, NH ₄ I, Al ₂ O ₃ , Eu ₂ O ₃ mixed, and added ethanol to fully grind, and then the raw material was heated at 60°C for drying; using solid state reaction, the ground raw material was surrounded by activated carbon powder and burned for 3 hours in a reducing atmosphere at a high temperature of 800°C, and the burning was completed The sample was cooled to room temperature with the furnace temperature; the sample was ground and sieved, washed twice with ethanol, and the sample was heated at 60°C for drying; the dried sample was mixed with methyl methacrylate solution of 1/2 of the sample mass, and the Dry at 120°C for 2 hours, then grind the sample and sieve it, wash it twice with ethanol, heat the sample at 60°C for drying, and then coat the screen.

Example 2

Taking Ca _0.5 SrZnY _0.5 FBr _0.7 I _0.3 :Pr _0.04 , Cd _0.05 as an example, according to the stoichiometric ratio, CaCO ₃ , SrCO ₃ , ZnO, Cd0, NH ₄ F, NH ₄ Br, NH ₄ I, Y ₂ O ₃ , Pr ₂ O ₃ mixed, and added ethanol to fully grind, and then the raw material was heated to 50°C for drying; using solid state reaction, the ground raw material was surrounded by activated carbon powder and burned in a reducing atmosphere at a high temperature of 800°C for 3 hours, and the burning was completed The sample was cooled to room temperature with the furnace temperature; the sample was ground and sieved, washed twice with ethanol, and the sample was heated at 60°C for drying; the dried sample was mixed with methyl methacrylate solution of 1/2 of the sample mass, and the Dry at 120°C for 2 hours, then grind the sample and sieve it, wash it twice with ethanol, heat the sample at 60°C for drying, and then coat the screen.

Claims (7)

1. Ca _1-xSrZnM _xFBr _1-yI _y: Re _z, Cd _0.05Light storage luminous material is characterized in that it is analytical pure that said raw material is selected purity for use, comprises CaCO ₃, SrCO ₃, ZnO, Cd0, NH ₄F, NH ₄Br, NH ₄I, the source of rare earth ion Re is by its oxide compound, halogenide, one of them is provided nitrate or vitriol; The source of the trivalent metal ion M that mixes is by its oxide compound, and one of them is provided halogenide or carbonate, and solvent is water or ethanol, and surperficial coating material is a methymethacrylate; Its chemical expression is:

Ca _1-xSrZnM _xFBr _1-yI _y:Re _z，Cd _0.05

Wherein, M is Al, In, a kind of element among Sc or the Y;

Re is rare earth ion: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, a kind of among Yb or the Lu;

X, y, the span of z is: 0.0001＜x≤0.6,0.0001＜y≤0.6; 0.0001＜z≤1.

2. according to the described Ca of claim 1 _1-xSrZnM _xFBr _1-yI _y: Re _z, Cd _0.05Light storage luminous material is characterized in that said

0.001＜x≤0.1，0.0001＜y≤0.1，0.0001＜z≤0.1。

3. according to claim 1 or 2 described Ca _1-xSrZnM _xFBr _1-yI _y: Re _z, Cd _0.05Light storage luminous material is characterized in that the chemical expression of said optical memory material is:

Ca _0.9SrZnAl _0.1FBr _0.9I _0.1:Eu _0.06，Cd _0.05。

4. according to claim 1 or 2 described Ca _1-xSrZnM _xFBr _1-yI _y: Re _z, Cd _0.05Light storage luminous material is characterized in that the chemical expression of said optical memory material is:

Ca _0.5SrZnY _0.5FBr _0.7I _0.3:Pr _0.04，Cd _0.05。

5. the Ca of a claim 1 _1-xSrZnM _xFBr _1-yI _y: Re _z, Cd _0.05The preparation method of light storage luminous material is characterized in that said preparation process is:

1) raw material is mixed according to stoichiometric ratio, and add solvent and fully grind, carry out drying again;

2) adopt solid state reaction, with ground raw material under 800-1400 ℃ of high temperature in the reducing atmosphere calcination 2-6 hour, the sample that calcination finishes was with the furnace temperature cool to room temperature;

3) will sieve after the sample grinding, and, sample is carried out drying with solvent wash twice;

4) the exsiccant sample is mixed with the methymethacrylate solution of sample quality 1/2,90--160 ℃ of oven dry 2 hours, after sieve after will sample grinding, and, sample is carried out drying can be coated with screen with solvent wash twice.

6. according to the described preparation method of claim 5, it is characterized in that said drying means is the heat drying method; Drying temperature is 0-160 ℃.

One of 7. according to claim 5 or 6 described preparation methods, it is characterized in that said calcination atmosphere is reducing atmosphere, below reducing atmosphere is selected to adopt: activity charcoal powder, graphite surrounds, the gas mixture of nitrogen or nitrogen and hydrogen.