CN100575454C - Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof - Google Patents
Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof Download PDFInfo
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- CN100575454C CN100575454C CN200810032494A CN200810032494A CN100575454C CN 100575454 C CN100575454 C CN 100575454C CN 200810032494 A CN200810032494 A CN 200810032494A CN 200810032494 A CN200810032494 A CN 200810032494A CN 100575454 C CN100575454 C CN 100575454C
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Abstract
The invention belongs to rare earth luminescent material technical field, be specifically related to the preparation method of the adulterated zinc phosphate orange red luminescent powder material of a kind of europium.The present invention adopts the solvent thermal reaction method, controls the synthetic of matrix zinc ammonium phosphate by the control solvent, adopts different tensio-active agents to control the pattern of product.This reaction process obtains orange red luminescent material by rational control reaction temperature, time and other conditions.Preparation method provided by the invention is simple, and is workable, has the characteristics of controllability and quantification, and the luminescent properties of products obtained therefrom is good; The product that present method obtains has regular appearance, and with the change of solvent and tensio-active agent, the pattern of product and luminescent properties all present regular variation.The product that the present invention makes can be widely used in fields such as power saving fluorescent lamp, luminous paint.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, be specifically related to the preparation method of the red luminescent powder material of the adulterated zinc ammonium phosphate of a kind of europium.
Background technology
The development of the fluorescent RE powder of China and applied research begin to have entered one in eighties of last century and develop period rapidly sixties, have researched and developed the fluorescent material of all kinds of large quantities of practicalities, have obtained the achievement of attracting attention.At present, the rare earth compound luminescent material has formed three big main products: information shows with fluorescent material, the phosphor of rare earth, long persistence luminescent powder.
In recent years, fast development along with nano science, new developing state has appearred in rare earth luminescent material, the character of nano luminescent material uniqueness has broad application prospects, if nano luminescent material can practicability will bring the dramatic change of field of light emitting materials, and the development of the relevant nano electron device of drive, as: nano level fluorescent powder grain can significantly improve the homogeneity that cathode tube is coated with screen, helps to improve its sharpness; And the nano level fluorescent material of feds (FED) usefulness is compared with traditional FED fluor, and it has little size and can be permeated fully by Low-voltage Electronic, thereby makes material be able to effective application.Specific surface area owing to nano-phosphor increases simultaneously, and the light-emitting particles number increases, thereby can reduce the consumption of rare-earth trichromatic fluorescent powder, thereby cost is reduced, and nano level fluorescent material is the preferred material that head light and indicating meter are coated with screen.The novel nano luminescent material has the advantage that meets the desired granularity of nano electron device.The confinement effect of nano material can Enhanced Radiation Reduced Blast transition speed and is excited transfer efficiency, and reducing along with particle size, excite in body quenching centre and the same particulate and unexcited luminescence center between the influence of cross-relaxation can reduce, can improve luminous efficiency. this all provides favourable condition for the practicability of nano luminescent material.Along with people to the going deep into of nano luminescent material understanding, the technological line of preparation nano luminescent material is abundant further.
At present, nano luminescent material preparation science and Developing Trend in Technology are the research of the process of tightening control, comprise that mainly the pattern (particle size, shape, surface and microstructure) to material controls mutually with thing, thereby reach the purpose that its property is studied and utilized.In the nano rare earth compound light-emitting preparation methods widely used have following several: solid reaction process, combustion method, sol-gel method, microemulsion method, the precipitator method, hydrothermal method.
Summary of the invention
The object of the present invention is to provide the preparation method of the orange red luminescent material of the adulterated zinc ammonium phosphate of europium that a kind of preparation method is easy, pattern is controlled.
The preparation method of the orange red luminescent material of the adulterated zinc ammonium phosphate of europium that the present invention proposes, concrete steps are as follows:
(1) proportioning raw materials:
Get 3～6mmolZn (NO
3)
26H
2O and 0.05～0.1mmolEu (NO
3)
36H
2O stirs with 10～15mL organic solvent dissolution, until the solution that forms clear, then, at room temperature stir 0.5～1 hour, and then add 1.05～2.1mmol primary ammonium phosphate to wherein adding 0.05～0.1g tensio-active agent, stirred 30～70 minutes, and obtained settled solution;
(2) solvent thermal building-up reactions:
The solution of step (1) gained is packed in the tetrafluoroethylene reactor, and under 100～170 ℃ temperature, crystallization 24～72 hours is at room temperature cooled off products therefrom then, filters, and promptly gets white solid;
(3) with step (2) gained white solid pure water, dehydrated alcohol repetitive scrubbing, drying promptly obtains desired product.
Among the present invention, the described organic solvent of step (1) is N,N-dimethylacetamide, N, in dinethylformamide or the pyrrolidone etc. any.
Among the present invention, the described tensio-active agent of step (1) be in cetyl trimethylammonium bromide or the polyoxyethylene glycol etc. any.
Among the present invention, drying temperature is 60～80 ℃ in the step (3), and be 24～36 hours time of drying.
The novel zinc ammonium phosphate that the present invention prepares is mixed the orange red luminescent powder material of europium, and luminescent properties is good.
The product that utilizes the inventive method to prepare can be widely used in field of light emitting materials such as power saving fluorescent lamp, luminous paint.
The product that present method obtains is workable, and products obtained therefrom can adopt the conventional sense means to detect.
Preparation method provided by the invention is simple, and is workable, has the characteristics of controllability and quantification, and the luminescent properties of products obtained therefrom is good; The product that present method obtains has regular appearance, and with the change of solvent and tensio-active agent, the pattern of product and luminescent properties all present regular variation.
Description of drawings
Fig. 1 is the XRD figure that the embodiment of the invention 1 gained zinc ammonium phosphate is mixed europium;
Fig. 2 is the fluorescence spectrum figure that the embodiment of the invention 1 gained zinc ammonium phosphate is mixed europium.
Fig. 3 is the transmission electron microscope picture that the embodiment of the invention 1 gained zinc ammonium phosphate is mixed europium.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
Get 6mmolZn (NO
3)
26H
2O and 0.1mmolEu (NO
3)
36H
2O 15mLN, the dissolving of N-N,N-DIMETHYLACETAMIDE is stirred until the solution that forms clear, adds the 0.1g cetyl trimethylammonium bromide then, at room temperature stirs 1 hour, adds the 2.1mmol primary ammonium phosphate again, stirs 1 hour.The liquid of above-mentioned gained is packed in the tetrafluoroethylene reactor, and crystallization is 72 hours under 160 ℃ of conditions.Cooling is at room temperature filtered then, obtains white precipitate, uses deionized water and dehydrated alcohol repetitive scrubbing at last.Then products obtained therefrom was descended dry 24 hours at 70 ℃, just can get white powder, be product.
Fig. 1 has provided the XRD figure that zinc ammonium phosphate is mixed europium, and the product that obtains as we know from the figure is six side's phases; Product has a hexagonal pattern as can be seen from Figure 3; As can be seen from Figure 2, the blood orange of zinc ammonium phosphate was good orange red luminescent material than nearly 1: 1.
Embodiment 2
Get 3mmolZn (NO
3)
26H
2O and 0.05mmolEu (NO
3)
36H
2O 10mLN, the dissolving of N-N,N-DIMETHYLACETAMIDE is stirred until the solution that forms clear, adds the 0.05g cetyl trimethylammonium bromide then, at room temperature stirs 30 minutes, adds the 1.05mmol primary ammonium phosphate again, stirs one hour.The liquid of above-mentioned gained is packed in the tetrafluoroethylene reactor, and crystallization is 24 hours under 100 ℃ of conditions.Cooling is at room temperature filtered then, obtains white precipitate, uses deionized water and dehydrated alcohol repetitive scrubbing at last.Then products obtained therefrom was descended dry 30 hours at 60 ℃, just can get white powder, be product.
Embodiment 3
Get 4mmolZn (NO
3)
26H
2O and 0.1mmolEu (NO
3)
36H
2O stirs until the solution that forms clear with the dissolving of 15mL pyrrolidone, adds the 0.1g polyoxyethylene glycol then, at room temperature stirs 70 minutes, adds the 1.433mmol primary ammonium phosphate again, stirs one hour.The liquid of above-mentioned gained is packed in the tetrafluoroethylene reactor, and crystallization is 72 hours under 170 ℃ of conditions.Cooling is at room temperature filtered then, obtains white precipitate, uses deionized water and dehydrated alcohol repetitive scrubbing at last.Then products obtained therefrom was descended dry 24 hours at 75 ℃, just can get white powder, be product.
Embodiment 4
Get 3mmolZn (NO
3)
26H
2O and 0.05mmolEu (NO
3)
36H
2O stirs until the solution that forms clear with the dissolving of 10mL pyrrolidone, adds the 0.05g polyoxyethylene glycol then, at room temperature stirred 1 hour, and added primary ammonium phosphate again, stirred 40 minutes, the liquid of above-mentioned gained is packed in the tetrafluoroethylene reactor, and crystallization is 36 hours under 120 ℃ of conditions.Cooling is at room temperature filtered then, obtains white precipitate, uses deionized water and dehydrated alcohol repetitive scrubbing at last.Then products obtained therefrom was descended dry 24 hours at 80 ℃, just can get white powder, be product.
Embodiment 5
Get 6mmolZn (NO
3)
26H
2O and 0.05mmolEu (NO
3)
36H
2O 15mLN, the dinethylformamide dissolving is stirred until the solution that forms clear, and the back adds an amount of polyoxyethylene glycol, at room temperature stirs 1 hour, adds primary ammonium phosphate again, stirs 70 minutes.The liquid of above-mentioned gained is packed in the tetrafluoroethylene reactor, and crystallization is 72 hours under 160 ℃ of conditions.Cooling is at room temperature filtered then, obtains white precipitate, uses deionized water and dehydrated alcohol repetitive scrubbing at last.Then products obtained therefrom was descended dry 24 hours at 75 ℃, just can get white powder, be product.
Embodiment 6
Get 5mmolZn (NO
3)
26H
2O and 0.05mmolEu (NO
3)
36H
2O 10mLN, the dissolving of N-N,N-DIMETHYLACETAMIDE is stirred until the solution that forms clear, and the back adds an amount of polyoxyethylene glycol, at room temperature stirs 50 minutes, adds the 1.8mmol primary ammonium phosphate again, stirs 1 hour.The liquid of above-mentioned gained is packed in the tetrafluoroethylene reactor, and crystallization is 48 hours under 130 ℃ of conditions, and cooling is at room temperature filtered then, obtains white precipitate, uses deionized water and dehydrated alcohol repetitive scrubbing at last.Then products obtained therefrom was descended dry 30 hours at 65 ℃, just can get white powder, be product.
Claims (2)
1, the preparation method of the adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium is characterized in that concrete steps are as follows:
(1) proportioning raw materials:
Get 3～6mmolZn (NO
3)
26H
2O and 0.05～0.1mmolEu (NO
3)
36H
2O stirs with 10～15mL organic solvent dissolution, until the solution that forms clear, then, at room temperature stir 0.5～1 hour, and then add 1.05～2.1mmol primary ammonium phosphate to wherein adding 0.05～0.1g tensio-active agent, stirred 30～70 minutes, and obtained settled solution;
(2) solvent thermal building-up reactions:
The solution of step (1) gained is packed in the tetrafluoroethylene reactor, and under 100～170 ℃ temperature, crystallization 24～72h at room temperature cools off products therefrom then, filters, and promptly gets white solid;
(3) with step (2) gained white solid pure water, dehydrated alcohol repetitive scrubbing, drying promptly obtains desired product; Wherein:
The described organic solvent of step (1) is N,N-dimethylacetamide, N, in dinethylformamide or the pyrrolidone any, described tensio-active agent be in cetyl trimethylammonium bromide or the polyoxyethylene glycol any.
2, the preparation method of the orange red luminescent material of the adulterated zinc ammonium phosphate of europium according to claim 1 is characterized in that drying temperature is 60～80 ℃ in the step (3), and be 24～36 hours time of drying.
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| CN200810032494A CN100575454C (en) | 2008-01-10 | 2008-01-10 | Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof |
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| CN200810032494A CN100575454C (en) | 2008-01-10 | 2008-01-10 | Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof |
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| CN100575454C true CN100575454C (en) | 2009-12-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335349A (en) * | 2000-07-21 | 2002-02-13 | 中国科学技术大学 | Rare earth subsulfate luminous material and its hot synthesis in solvent |
| CN1460637A (en) * | 2003-04-09 | 2003-12-10 | 广西大学 | Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction |
| CN1635049A (en) * | 2004-11-26 | 2005-07-06 | 兰州大学 | Vacuum ultraviolet energized red fluorescent material and process for preparation |
| CN1721585A (en) * | 2005-05-24 | 2006-01-18 | 吉林大学 | Preparation method of water soluble manganese added zinc sulfide nano-crystalline with high fluorescence efficiency |
-
2008
- 2008-01-10 CN CN200810032494A patent/CN100575454C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335349A (en) * | 2000-07-21 | 2002-02-13 | 中国科学技术大学 | Rare earth subsulfate luminous material and its hot synthesis in solvent |
| CN1460637A (en) * | 2003-04-09 | 2003-12-10 | 广西大学 | Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction |
| CN1635049A (en) * | 2004-11-26 | 2005-07-06 | 兰州大学 | Vacuum ultraviolet energized red fluorescent material and process for preparation |
| CN1721585A (en) * | 2005-05-24 | 2006-01-18 | 吉林大学 | Preparation method of water soluble manganese added zinc sulfide nano-crystalline with high fluorescence efficiency |
Non-Patent Citations (1)
| Title |
|---|
| Matrix Induced Synthesis of Eu3 + Doped Zn3 ( PO4 ) 2andLaPO4Phosphors by in2Situ Composing Hybrid Precursors. Xiao Xiuzhen et al.J OURNAL OF RARE EARTHS,Vol.23 No.Suppl. 2005 * |
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