CN1304525C

CN1304525C - Zinc sulfate based long persistence fluorescent powder and its preparation

Info

Publication number: CN1304525C
Application number: CN 02136365
Authority: CN
Inventors: 徐国庆
Original assignee: Individual
Current assignee: Individual
Priority date: 2002-08-02
Filing date: 2002-08-02
Publication date: 2007-03-14
Anticipated expiration: 2022-08-02
Also published as: CN1472277A

Abstract

The present invention relates to a long-persistence light-storing fluorescent powder which takes zinc sulfate as a matrix, and conventional industrial zinc sulfate crystal is adopted as a base. The present invention is characterized in that after substances, such as sodium chloride, magnesium chloride, silver sulfate, indium nitrate, etc., are added with a special preparation process, the long-persistence light-storing fluorescent powder avoids the requirements for high temperature of more than 1300 DEG C, reinforced crushing ball mill processing, etc., and the aftercurrent glow time of the light-storing fluorescent powder is more than 12 hours. The material can be widely used in noctilucent printing ink, noctilucent paint, noctilucent plastic, noctilucent glass printing and coating and can be manufactured into indications of various door plates, road signs, safety alarm plates, etc., and the material can also be used in low-light level light sources, decorative products such as artware, religious decoration, mascots, etc.

Description

It with zinc sulfate steady persistence luminous storage fluorescence powder of matrix and preparation method thereof

It is the steady persistence luminous storage fluorescence powder and preparation method thereof of matrix with zinc sulfate that technical field the present invention relates to a kind of.Belong to the luminescent material technical field.

The background technology luminous storage fluorescence powder be a kind of after the sun or other light source irradiation, have hold optical property, in the dark can send for a long time residual light, can repeatedly repeat to hold light and luminous again material.Luminous storage fluorescence powder mostly was sulfide-based compound in the past, ZnS: Cu, Co or CaS: Ce etc. for example, between the residual light time of this class luminous storage fluorescence powder generally at 1～2 hour to tens hours, and the weak chemical of sulfide-based compound has determined them not water-fast, easily aging, problem such as work-ing life is short.Another kind of luminous storage fluorescence powder contains radioactive substance, owing to known reason is forbidden by the world.

It is the luminous storage fluorescence powder of matrix that earlier 1990s has begun to occur with the alkali earth metal aluminate.This class can be reached more than 24 hours between the residual light time by the luminosity height of Eu activated aluminate luminous storage fluorescence powder, and excellent in stability, and moisture-proof, anti-sunlight are exposed to the sun, and the life-span is long, thereby obtains to use in every field.But, this class aluminate luminous storage fluorescence powder, the most employing in industrial-scale production at present with α-Al ₂O ₃After the compound of several necessary components, by the high temperature solid state reaction more than 1300 ℃, in this case, the final product that obtains is the scleroma piece of ceramic-like often, and this is because α-Al ₂O ₃Chemically reactive very low, only under enough high-temperatures, could interact with the compound of other component such as alkaline-earth metal, generate the monoclinic form aluminate, and make rare-earth activated dose as Eu ₂O ₃Deng entering lattice, form luminescence center and electronics deep trap.Must could arrive actual tens microns the powder that requires through powerful processing such as ball mill pulverizer for this rock-hard product.And such result must make light-emitting crystal structures be subjected to a certain degree destruction, produces many defectives.These defectives can absorb and excite luminous energy and few luminous.As continue to pulverize carefully below 10 μ m, brightness just sharply descends, and residual light is decay fast also, more carefully below 3 μ m, the luminous practicality that has lost it that it is faint.

Summary of the invention In view of the foregoing the objective of the invention is: both adopted conventional industrial sulphuric acid zinc-base material, and after adding material such as sodium-chlor and magnesium chloride, Sulfuric acid disilver salt and indium nitrate and special preparation technology, it is overcritical that acquisition avoids that high temperature more than 1300 ℃ and powerful ball mill pulverizer etc. handle etc., still makes luminous storage fluorescence powder of the present invention reach effect more than 12 hours between the residual light time.，

Embodiment

Base-material: adopt conventional industrial sulphuric acid zinc crystallization (H ₇O ₂) its purity is more than 98%;

(1) adopts the high impurity of zinc sulfate content few (interior not iron content, manganese impurity), not then adopt to add oxygenant such as potassium permanganate solution (potassium permanganate solution: potassium permanganate adds 33～43 ℃ of water of temperature, and its concentration is controlled at 32～34%) with the iron in precipitating in it, manganese impurity;

(2) about 3.5, begin oxidation heating (80 ℃) at PH;

(3) adjust sedimentation and filtration through zinc sulphide, consider and remove residue;

(4) add sulfuric acid to adjust its PH to 5;

(5) add sulfuration ammonia and stir, zinc sulfate is further precipitated, (at this moment, powder contains outside the zinc sulfate, also has 7% sulphur--be referred to as many zinc sulphide) consider done in pressurization;

(6) with weight ratio, add 0.005 sodium-chlor and 0.005 magnesium chloride respectively by 1000 parts in many zinc sulphide, add 0.32 Sulfuric acid disilver salt and 0.62 indium nitrate simultaneously and mix;

(7) heat to about 800 ℃, carry out roasting and--cool off--pulverizing--fine screen.The fluorescent material of back gained has the good photosensitiveness that holds, and can arrive more than 12 hours between the residual light time.

In sum as can be known, of the present invention a kind of be the steady persistence luminous storage fluorescence powder of matrix with zinc sulfate, though adopted conventional industrial sulphuric acid zinc crystallization as base-material.But it splits path in addition, after adding material such as sodium-chlor and magnesium chloride, Sulfuric acid disilver salt and indium nitrate and special preparation technology, obtained both to avoid the overcritical of high temperature more than 1300 ℃ and powerful ball mill pulverizer processing etc., still made the effect that arrives between residual light time of its luminous storage fluorescence powder more than 12 hours.

But material widespread use of the present invention, for example luminescent ink, luminescent coating, luminous plastics, noctilucence glass printing, the indication that is coated with and makes various doorplates, road sign, security warning board etc., decorative kind product such as workmanship, religion and mascot and at aspects such as low-light (level) light sources.

Claims

1, with zinc sulfate is the steady persistence luminous storage fluorescence powder of matrix, it is characterized in that except that matrix, also containing at least a muriate, material such as Sulfuric acid disilver salt and indium nitrate, and with weight ratio is to add 0.5% sodium-chlor and 0.5% magnesium chloride in 98% the zinc sulfate crystallization 1000 by matrix purity; Add 0.32 Sulfuric acid disilver salt and 0.62 indium nitrate simultaneously.

2, as claimed in claim 1 is the steady persistence luminous storage fluorescence powder its preparation method of matrix with zinc sulfate, it is characterized in that adding potassium permanganate solution in the crystallization of matrix zinc sulfate;

Employing matrix purity is 98% zinc sulfate crystallization, and zinc sulfate iron content, manganese impurity then adopt and adds oxygenant such as potassium permanganate solution;

Potassium permanganate solution: potassium permanganate adds the water of 33～43 ℃ of temperature, and its concentration is controlled at 32～34% by weight; With the iron in precipitating in it, manganese impurity,, PH is heated to 80 ℃ when beginning oxidation about 3.5;

Adjust sedimentation and filtration through zinc sulphide, consider and remove residue;

Add sulfuric acid to adjust its PH to 5;

Add sulfuration ammonia and stir, zinc sulfate is further precipitated, the back pressurization is considered dried, and at this moment, powder contains outside the zinc sulfate, also has 7% sulphur---be referred to as many zinc sulphide;

With weight ratio, add 0.5% sodium-chlor and 0.5% magnesium chloride respectively by many zinc sulphide 1000; Add the mixing of 0.32 Sulfuric acid disilver salt and 0.62 indium nitrate simultaneously and heat, carry out roasting and---cool off---pulverizing---fine screen to 800 ℃.