CN1352225A - Process for preapring manganese zinc sulfide blended nanometer fluorescent powder in batchs - Google Patents
Process for preapring manganese zinc sulfide blended nanometer fluorescent powder in batchs Download PDFInfo
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- CN1352225A CN1352225A CN 01138748 CN01138748A CN1352225A CN 1352225 A CN1352225 A CN 1352225A CN 01138748 CN01138748 CN 01138748 CN 01138748 A CN01138748 A CN 01138748A CN 1352225 A CN1352225 A CN 1352225A
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Abstract
The process of preparing nanometer fluorescent ZnS:Mn powder includes: reaction between methacrylic acid and zinc acetate to prepare zinc methacrylate; polymerization of zinc methacrylate under the action of chain transferring agent and primer with the polymerization degree and thus the nanometer particle size being controlled by regulating the molar ratio between chain transferring agent and primer; reaction between polyzinc methacrylate and Na2S; and the centrifugal separation, washing and drying of the reaction product to obtain the nanometer fluorescent ZnS:Mn powder. During forming nanometer particle, nanometer particle is cladded by polyzinc methacrylate and this results in pure surface of nanometer particle, high fluorescent efficiency and long service life of nanometer fluorescent powder. The process of the present invention has lower cost, simple operation and no toxicity.
Description
One, technical field: the invention belongs to the semiconductive luminescent materials technical field, relate to a kind of preparation method of metal-doped ZnS base nano luminescent material.
Two, background technology: well-known, ZnS is a kind of luminescent material matrix of unique properties, by changing the efficient visible radiation that wherein doping agent can obtain different-waveband, realizes truly panchromatic luminous.Therefore, the ZnS material has obtained using extremely widely.In decades, people improve its luminous efficiency for realizing panchromaticization of ZnS based luminescent material, improve its photoelectric properties, and opening up its application has carried out a lot of effort, has obtained immense success.Particularly 1994, Bhargava reported in nanometer ZnS matrix and has mixed Mn
2+The back finds that its quantum yield is improved largely, and this has caused the enthusiasm that people study ZnS base nano luminescent material greatly.In recent years, people have adopted several different methods to be used to prepare metal-doped ZnS base nano luminescent material, have obtained remarkable progress.In the chitosan organic medium, made ZnS as human complexing transformation approach such as the Jin Yan of Shanghai university: the Cu nano microcrystalline, the grandson of Peking University listens people such as east and adopts water-sol synthesis method to prepare ZnS: the Cu water-sol, people such as the Li Zhen of University Of Tianjin steel make medium with polyoxyethylene, have successfully mixed multiple elements such as europium, manganese, copper in the ZnS nano microcrystalline.But these explore the batch preparations all fail to realize metal-doped ZnS base nano-phosphor, and products obtained therefrom need rely on carrier such as solution or film and can not independently exist with the crystallite shape, thereby its application is restricted.Metal-doped ZnS base nano-phosphor batch preparations still has very, and large space wait people go to explore.
Three, Fa Ming content: it is simple to the objective of the invention is to set up a kind of equipment, easy to operate, cost is low, luminous efficiency is high, can produce manganese-doped zinc sulfide nano fluorescent powder, preparation method thereof in batches.The present invention realizes by following reactions steps:
(1) preparation of zinc methacrylate
According to equation [I], the reaction by methacrylic acid and zinc acetate prepares zinc methacrylate;
(2) preparation of polymethyl acrylic acid zinc
According to reaction formula [II], make zinc methacrylate polymerization reaction take place under chain-transfer agent and action of evocating, by regulating the mol ratio of chain-transfer agent and methacrylic acid, come the controlled polymerization degree, thus the particle diameter of control nanoparticle, n is the polymerization degree;
(3) ZnS: the preparation of Mn nano-phosphor
According to reaction formula [III], make polymethyl acrylic acid zinc and Na
2S, MnSO
4Reaction, products therefrom can obtain ZnS after centrifugation, washing, drying: the Mn nano-phosphor;
Advantage of the present invention is:
(1) realized ZnS first: the batch preparations of Mn nano-phosphor.
(2) present method cost is low, and is simple to operate, and nontoxicity, pollution-free.
(3) by regulating the mol ratio of chain-transfer agent and methacrylic acid, can control the particle diameter of nanoparticle within the specific limits.Meanwhile, in the nanoparticle forming process, polymethyl acrylic acid coats the nanoparticle that generates, thus passivation nanoparticle surface, luminous efficiency has been improved about 30%, and has prolonged the work-ing life of material.
Four. embodiment: the present invention is as follows according to the specific embodiment of reaction formula [I], reaction formula [II] and reaction formula [III]:
Embodiment 1: with 40ml water, 0.03mol zinc acetate and the methacrylic acid of 5.5ml be added in the there-necked flask that has prolong, heat up and stir, when temperature rises to 60 ℃, the persulfate aqueous solution that in flask, adds 40ml 0.05M, stir after 5 minutes, in there-necked flask, add the Thiovanic acid (mol ratio of methacrylic acid and Thiovanic acid is 1: 200) of 20ml 0.017M, reacted one hour down at 80 ℃.Treat that temperature is cooled to 50 ℃, in reactant, add the MnSO of 20ml 0.06M
4The aqueous solution, the Na of dropping 40ml 0.SM in 30 minutes then
2The S aqueous solution makes reaction mixture continue reaction 30 minutes at 80 ℃.Under the room temperature reaction mixture is carried out centrifugation, use the methanol wash products therefrom, vacuum-drying can obtain ZnS: the Mn nanometer powder.Particle diameter is 2nm.
Embodiment 2: change the Thiovanic acid described in the embodiment 1 and the molal quantity of methacrylic acid, making its mol ratio is 1: 250, and other concrete operations can get the ZnS that particle diameter is 2.2nm: the Mn nano-phosphor as described in the embodiment 1.
Claims (3)
1, a kind of preparation method who is suitable for producing in batches the manganese-doped zinc sulfide nano-phosphor is characterized in that: adopts methacrylic acid and zinc acetate as start material, carries out polymerization and vulcanization reaction in certain temperature then,
(1) preparation of zinc methacrylate: according to reaction formula [I], the reaction by methacrylic acid and zinc acetate prepares zinc methacrylate;
(2) preparation of polymethyl acrylic acid zinc salt: according to reaction formula [II], make zinc methacrylate polymerization reaction take place under chain-transfer agent and action of evocating, by regulating the mol ratio of chain-transfer agent and methacrylic acid, come the regulating and controlling polymerization degree n, thereby nanometer particle size is controlled;
(3) according to reaction formula [III], make polymethyl acrylic acid zinc and Na
2S, MnSO
4Reaction, products therefrom can obtain ZnS after centrifugation, washing, drying: the Mn nano-phosphor;
2, the preparation method of manganese-doped zinc sulfide nano-phosphor according to claim 1 is characterized in that: according to reaction formula [I] and reaction formula [III], the mol ratio of zinc acetate and manganous sulfate is 100: 2-10.
3, the preparation method of manganese-doped zinc sulfide nano-phosphor according to claim 1 is characterized in that: adopt Potassium Persulphate or ammonium persulphate or dibenzoyl peroxide or Diisopropyl azodicarboxylate according to the initiator in the reaction formula [II]; Chain-transfer agent adopts Thiovanic acid or thiohydracrylic acid etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011387483A CN1180051C (en) | 2001-11-30 | 2001-11-30 | Process for preapring manganese zinc sulfide blended nanometer fluorescent powder in batchs |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011387483A CN1180051C (en) | 2001-11-30 | 2001-11-30 | Process for preapring manganese zinc sulfide blended nanometer fluorescent powder in batchs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1352225A true CN1352225A (en) | 2002-06-05 |
| CN1180051C CN1180051C (en) | 2004-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011387483A Expired - Fee Related CN1180051C (en) | 2001-11-30 | 2001-11-30 | Process for preapring manganese zinc sulfide blended nanometer fluorescent powder in batchs |
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| CN (1) | CN1180051C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476160B (en) * | 2008-12-17 | 2011-08-10 | 陕西科技大学 | Ultrasonic aging synthesis for manganese doped zinc sulphide nanocrystalline |
| CN101747574B (en) * | 2008-11-28 | 2012-01-18 | 复旦大学 | Transparent fluorescent film, preparation method and application thereof |
-
2001
- 2001-11-30 CN CNB011387483A patent/CN1180051C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747574B (en) * | 2008-11-28 | 2012-01-18 | 复旦大学 | Transparent fluorescent film, preparation method and application thereof |
| CN101476160B (en) * | 2008-12-17 | 2011-08-10 | 陕西科技大学 | Ultrasonic aging synthesis for manganese doped zinc sulphide nanocrystalline |
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| Publication number | Publication date |
|---|---|
| CN1180051C (en) | 2004-12-15 |
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