CN100362079C - Spheroidal structure fluorophor preparation method - Google Patents
Spheroidal structure fluorophor preparation method Download PDFInfo
- Publication number
- CN100362079C CN100362079C CNB2006100416671A CN200610041667A CN100362079C CN 100362079 C CN100362079 C CN 100362079C CN B2006100416671 A CNB2006100416671 A CN B2006100416671A CN 200610041667 A CN200610041667 A CN 200610041667A CN 100362079 C CN100362079 C CN 100362079C
- Authority
- CN
- China
- Prior art keywords
- preparation
- fluor
- mixing solutions
- electric spinning
- metal salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a spheroidal structure fluorophor preparation method. Firstly, the required metal salt which is used for preparing the fluorophor is respectively dissolved into deionized water, then, according to the molar ratio of metallic elements in the fluorophor which is prepared as the requirement, the metal salt solution is mixed and is uniformly stirred to be mixed solution and is filled with water-solubility polymer materials; the metal salt solution is arranged in a glass pipe of an electric spinning device for electric spinning, electric spinning films which are obtained by the electric spinning are arranged in a muffle furnace, and the electric spinning films are roasted for 2 to 4 hours under the temperature from 1100DEG. C to 1400DEG. C. The present invention can obtain micron/nanospheres of regular metal salt and high molecular mixtures by adopting the solution which is prepared by high-voltage spinning; by high-temperature roasting, as the removal of high molecular components, the products still remain the patterns of the micron/nanosphere shape in the process of the high-temperature roasting, and the diameter is further lessened. Accordingly, the fluorophor in the structure of the micron/nanosphere shape is obtained.
Description
Technical field
The invention belongs to the geseous discharge technical field, be specifically related to a kind of preparation method of ball-like structure fluor.
Background technology
In recent years, in the employed colour display device of pictorial display such as computer and TV, the display unit of using plasma display panel enjoys as realizing the colour display device of large-scale and slim light weight gazes at.
In order to carry out panchromatic demonstration, in plasm display device, has the luminescent coating that sends each coloured light of three primary colors (red (R), green (G), blue (B)), the fluorophor particle that constitutes luminescent coating is subjected to interior produce ultraviolet ray excited of plasma display system discharge cell, produces visible light of all kinds.The common method that fluorophor particle is coated on the plasma display panel is a silk screen print method, and in the method, the shape of the luminescent coating that is coated with seriously is subjected to the condition influence of single phosphor particle shape, formula of size and coating process.As everyone knows, the more aspheric fluor of spheric phosphor particle has higher filling efficient, and the particle diameter of fluor little and even (size distribution unanimity) obtains more beautiful coated side easily.In addition, spherical small-particle fluor has increase brightness, improves resolving power, and it is few to be coated with when screen fluor consumption, serial advantages such as the closely knit and high conformity of coating.
Up to now, people have made a lot of effort in the spherical small-particle fluor of preparation, adopted various method, as: sol-gel method, chemical coprecipitation, spray pyrolysis, combustion method etc.
But the available fluor that is used for plasma panel does not have above-mentioned desirable particle characteristics at present, and their majorities are irregularly shaped or sheet.Report about spherical particle phosphor preparation method is also arranged in the document on a small quantity, but resulting phosphor particle particle diameter big (2 μ m～10 μ m), shape and irregular are prone to agglomeration between particle simultaneously.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method of ball-like structure fluor is provided, the spherical pattern of micrometer/nanometer that the fluor that makes by preparation method of the present invention has rule, and particle diameter is between 500nm～2 μ m, this fluor is used for the plasma panel manufacture craft, can form that coating is closely knit, the luminescent coating of high conformity, help increasing screen intensity, improve resolving power.
For achieving the above object, the technical solution used in the present invention is: at first, preparation fluor required metal-salt is dissolved in respectively is mixed with the solution that concentration is 3～8mol/L in the deionized water, then with metal salt solution by the mixed in molar ratio of the metallic element in the fluor of required preparation and stir and make mixing solutions; Secondly, add water-soluble high-molecular material polyvinylpyrrolidone, polyoxyethylene or polyvinyl alcohol in above-mentioned mixing solutions, dissolve and stir, the viscosity that makes mixing solutions is 20mPas～30mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under 8cm～20cm it is applied 8kV～12kV, behind electrospinning 20min～60min, on the dash receiver of electric spinning equipment, obtain metal-salt and high molecular mixture electrospinning film; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1100 ℃～1400 ℃ following roasting 2h～4h.
Metal-salt of the present invention is Ba (NO
3)
2, Al (NO
3)
3, Mn (CH
3COO)
2, Gd (NO
3)
3, Y (NO
3)
3, B (NO
3)
3, EuSO
4, Eu (NO
3)
3, Lu (NO
3)
3, Sc2 (SO
4)
3, Sb (NO
3)
3, ZnSO
4, MnSO
4, Ca (NO
3)
2, Sr
2CO
3, Mg (NO
3)
2, Re (NO
3)
3, Ce (SO
4)
2, PbSO
4Or Li
2CO
3Fluor is rouge and powder: Y
2O
3: Eu, (Y, Gd) BO
3: Eu, YBO
3: Eu, GdBO
3: Eu, LuBO
3: Eu, ScBO
3: Eu or Y
2SiO
5: Eu; Green powder: BaAl
12O
19: Mn, Zn
2SiO
4: Mn, SrAl
12O
19: Mn, CaAl
12O
19: Mn or BaMgAl
14O
23: Mn or blue powder: BaMgAl
10O
17: Eu, BaMgAl
14O
23: Eu, Y
2SiO
5: Ce or CaWO
4: Pb.
Because the solution that the present invention adopts the high pressure electrospinning to be prepared, can access the metal-salt and the high molecular mixture micrometer/nanometer ball of rule, pass through high-temperature roasting again, in the process of high-temperature roasting, removal along with high molecular component, product still keeps the spherical pattern of micrometer/nanometer, and diameter further diminishes, thereby obtains the fluor of micrometer/nanometer ball-like structure.
Embodiment
Embodiment 1, at first, and with the Y (NO of preparation fluor
3)
3And Eu (NO
3)
3Be dissolved in respectively and be mixed with the metal salt solution that concentration is 8mol/L in the deionized water, then metal salt solution is pressed Y
2O
3: the mixed in molar ratio of metallic element and stir and make mixing solutions among the Eu; Secondly, adding water-soluble polymer polyvinylpyrrolidone (PVP) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 26mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 15cm it is applied 9kV, behind the electrospinning 30min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1100 ℃ of following roasting 2h.
Embodiment 2, at first, and with the Gd (NO of preparation fluor
3)
3, B (NO
3)
3And Eu (NO
3)
3Be dissolved in respectively and be mixed with the metal salt solution that concentration is 5mol/L in the deionized water, then metal salt solution is pressed GdBO
3: the mixed in molar ratio of the metallic element among the Eu also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyoxyethylene (PEO) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 22mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 10cm it is applied 11kV, behind the electrospinning 45min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1300 ℃ of following roasting 3h.
Embodiment 3, at first, and with the Ba (NO of preparation fluor
3)
2, Al (NO
3)
3And Mn (CH
3COO)
2Be dissolved in respectively and be mixed with the metal salt solution that concentration is 6mol/L in the deionized water, then metal salt solution is pressed BaAl
12O
19: the mixed in molar ratio of the metallic element among the Mn also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyvinyl alcohol (PVA) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 28mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 8cm it is applied 10kV, behind the electrospinning 28min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed on then in the luxuriant good fortune stove, get final product at 1200 ℃ of following roasting 4h.
Embodiment 4, at first, and with the Ba (NO of preparation fluor
3)
2, Mg (NO
3)
2, Al (NO
3)
3And Mn (CH
3COO)
2Be dissolved in respectively and be mixed with the metal salt solution that concentration is 3mol/L in the deionized water, then metal salt solution is pressed BaMgAl
14O
23: the mixed in molar ratio of the metallic element among the Mn also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyvinylpyrrolidone (PVP) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 30mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 20cm it is applied 8kV, behind the electrospinning 60min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1400 ℃ of following roasting 4h.
Embodiment 5, at first, and with the Sr of preparation fluor
2CO
3, Al (NO
3)
3And MnSO
4Be dissolved in respectively and be mixed with the metal salt solution that concentration is 4mol/L in the deionized water, then metal salt solution is pressed SrAl
12O
19: the mixed in molar ratio of the metallic element among the Mn also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyoxyethylene (PEO) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 20mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 12cm it is applied 12kV, behind the electrospinning 50min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1150 ℃ of following roasting 2h.
Embodiment 6, at first, and with the Ca (NO of preparation fluor
3)
2, Al (NO
3)
3And Mn (CH
3COO)
2Be dissolved in respectively and be mixed with the metal salt solution that concentration is 7mol/L in the deionized water, then metal salt solution is pressed CaAl
12O
19: the mixed in molar ratio of the metallic element among the Mn also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyvinyl alcohol (PVA) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 25mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 17cm it is applied 8kV, behind the electrospinning 20min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1250 ℃ of following roasting 3h.
Embodiment 7, at first, and with the Ba (NO of preparation fluor
3)
2, Mg (NO
3)
2, Al (NO
3)
3, and EuSO
4Be dissolved in respectively and be mixed with the metal salt solution that concentration is 3mol/L in the deionized water, then metal salt solution is pressed BaMgAl
10O
17: the mixed in molar ratio of the metallic element among the Eu also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyvinylpyrrolidone (PVP) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 27mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 13cm it is applied 10kV, behind the electrospinning 35min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1350 ℃ of following roasting 3h.
Embodiment 8, at first, and with the Ba (NO of preparation fluor
3)
2, Mg (NO
3)
2, Al (NO
3)
3And EuSO
4Be dissolved in respectively and be mixed with the metal salt solution that concentration is 8mol/L in the deionized water, then metal salt solution is pressed BaMgAl
14O
23: the mixed in molar ratio of the metallic element among the Eu also stirs and makes mixing solutions; Secondly, adding water-soluble polymer polyvinyl alcohol (PVA) dissolves and stirs in above-mentioned mixing solutions, and the viscosity that makes mixing solutions is 23mPas; Once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under the 19cm it is applied 12kV, behind the electrospinning 55min, obtains metal-salt and high molecular mixture electrospinning film on the dash receiver of electric spinning equipment; At last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1100 ℃ of following roasting 2h.
The fluor that obtains according to preparation method of the present invention still keeps the spherical pattern of micrometer/nanometer, and diameter is littler than presoma, is 500nm～2 μ m.
Claims (3)
1. the preparation method of a ball-like structure fluor is characterized in that:
1) at first, preparation fluor required metal-salt is dissolved in respectively is mixed with the solution that concentration is 3～8mol/L in the deionized water, then with metal salt solution by the mixed in molar ratio of the metallic element in the fluor of required preparation and stir and make mixing solutions;
2) secondly, add water-soluble high-molecular material polyvinylpyrrolidone, polyoxyethylene or polyvinyl alcohol in above-mentioned mixing solutions, dissolve and stir, the viscosity that makes mixing solutions is 20mPas～30mPas;
3) once more, the mixing solutions that is added with water-soluble high-molecular material is placed the Glass tubing of electric spinning equipment, in interelectrode distance is the high pressure that under 8cm～20cm it is applied 8kV～12kV, behind electrospinning 20min～60min, on the dash receiver of electric spinning equipment, obtain metal-salt and high molecular mixture electrospinning film:
4) last, take the electrospinning film on the dash receiver off, be placed in the luxuriant good fortune stove, get final product at 1100 ℃～1400 ℃ following roasting 2h～4h.
2. the preparation method of ball-like structure fluor according to claim 1 is characterized in that: said metal-salt is Ba (NO
3)
2, Al (NO
3)
3, Mn (CH
3COO)
2, Gd (NO
3)
3, Y (NO
3)
3, B (NO
3)
3, EuSO
4, Eu (NO
3)
3, Lu (NO
3)
3, Sc
2(SO
4)
3, Sb (NO
3)
3, ZnSO
4, MnSO
4, Ca (NO
3)
2, Sr
2CO
3, Mg (NO
3)
2, Re (NO
3)
3, Ce (SO
4)
2, PbSO
4Or Li
2CO
3
3. the preparation method of ball-like structure fluor according to claim 1 is characterized in that: said fluor is rouge and powder: Y
2O
3: Eu, (Y, Gd) BO
3: Eu, YBO
3: Eu, GdBO
3: Eu, LuBO
3: Eu, ScBO
3: Eu, Y
2SiO
5: Eu; Green powder: BaAl
12O
19: Mn, Zn
2SiO
4: Mn, SrAl
12O
19: Mn, CaAl
12O
19: Mn, BaMgAl
14O
23: Mn or blue powder: BaMgAl
10O
17: Eu, BaMgAl
14O
23: Eu, Y
2SiO
5: Ce or CaWO
4: Pb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100416671A CN100362079C (en) | 2006-01-13 | 2006-01-13 | Spheroidal structure fluorophor preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100416671A CN100362079C (en) | 2006-01-13 | 2006-01-13 | Spheroidal structure fluorophor preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1800300A CN1800300A (en) | 2006-07-12 |
| CN100362079C true CN100362079C (en) | 2008-01-16 |
Family
ID=36810517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100416671A Expired - Fee Related CN100362079C (en) | 2006-01-13 | 2006-01-13 | Spheroidal structure fluorophor preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100362079C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371723B (en) * | 2014-11-12 | 2016-09-14 | 河北利福化工科技有限公司 | A kind of white light LEDs preparation method of efficient class ball-type green emitting phosphor |
| CN109505065A (en) * | 2019-01-11 | 2019-03-22 | 天津工业大学 | A kind of photochromic nano tunica fibrosa and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1275757A2 (en) * | 2001-07-13 | 2003-01-15 | Transmit Gesellschaft für Technologietransfer mbH | Tubes with inside diameters on the nanometric scale |
| CN1456360A (en) * | 2003-05-28 | 2003-11-19 | 东南大学 | Absorbable superfine fibre tissue remedial materials and preparing method thereof |
| CN1546754A (en) * | 2003-12-04 | 2004-11-17 | 东南大学 | Twisted ultra-fine nanometer fiber film material and preparing method thereof |
| WO2004112183A1 (en) * | 2003-06-17 | 2004-12-23 | Samshin Creation Co., Ltd. | A complex membrane for electrochemical device, manufacturing method and electrochemical device having the same |
| CN1584135A (en) * | 2004-05-31 | 2005-02-23 | 吉林大学 | Electrical spinning method for making metal nanometer particles in order in high-polymer nanometer fibre |
-
2006
- 2006-01-13 CN CNB2006100416671A patent/CN100362079C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1275757A2 (en) * | 2001-07-13 | 2003-01-15 | Transmit Gesellschaft für Technologietransfer mbH | Tubes with inside diameters on the nanometric scale |
| CN1456360A (en) * | 2003-05-28 | 2003-11-19 | 东南大学 | Absorbable superfine fibre tissue remedial materials and preparing method thereof |
| WO2004112183A1 (en) * | 2003-06-17 | 2004-12-23 | Samshin Creation Co., Ltd. | A complex membrane for electrochemical device, manufacturing method and electrochemical device having the same |
| CN1546754A (en) * | 2003-12-04 | 2004-11-17 | 东南大学 | Twisted ultra-fine nanometer fiber film material and preparing method thereof |
| CN1584135A (en) * | 2004-05-31 | 2005-02-23 | 吉林大学 | Electrical spinning method for making metal nanometer particles in order in high-polymer nanometer fibre |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1800300A (en) | 2006-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100396753C (en) | Plasma display unit, phosphor and process for producing phosphor | |
| KR100550721B1 (en) | Phosphor and method for production thereof and plasma display device | |
| KR100547308B1 (en) | Plasma display device, production method therefor, phosphor ink, and manufacturing method for phosphor | |
| US7053551B2 (en) | Zinc silicate system phosphor, method for producing the same, zinc silicate system phosphor paste, and display device | |
| CN102766457A (en) | Preparation method for yttrium gadolinium europium oxide red fluorescent powder applicable to 3D PDP | |
| CN100362079C (en) | Spheroidal structure fluorophor preparation method | |
| CN102212360B (en) | Field emission fluorescent material and preparation method thereof | |
| KR100714223B1 (en) | Plasma display and method for producing phosphor used therein | |
| CN101845303A (en) | Method for preparing vacuum ultraviolet excited green aluminate fluorescent powder | |
| JP3690377B2 (en) | Method for manufacturing phosphor | |
| KR100714222B1 (en) | Plasma display and method for producing phosphor used therein | |
| JP2002194347A (en) | Fluorescent substance, method for producing the same and luminous device | |
| CN103773362A (en) | Calcium metasilicate luminous material and preparation method for same | |
| CN1408812A (en) | Borate red fluorescent powder for color plasma plate display and its producing method | |
| CN102352249A (en) | (Y1-x-yGdy,Eux)(P1-a,Va)O4 red phosphor and preparation method thereof | |
| CN1285704C (en) | Nano fluorescent powder and preparing method thereof | |
| CN101012377A (en) | Green light fluorescent powder for PDP and preparing method | |
| CN111718712A (en) | Eu (Eu)3+/Tb3+Co-doped SiO2Ribbon fiber film luminescent material and preparation method thereof | |
| CN101696356A (en) | Method for manufacturing borate green emitting phosphor | |
| CN108946788A (en) | A kind of preparation method of needle-shaped yttrium oxide | |
| CN100396752C (en) | Plasma display device | |
| CN101302426A (en) | Fluorescent powder for field emission and preparation thereof | |
| CN100454476C (en) | Plasma display and method for manufacturing same | |
| CN101182413B (en) | Method for preparing rare earth aluminate matrix fluorescent powder | |
| JP2005183246A (en) | Plasma display unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SICHUAN SHIJI SHUANGHONG DISPLAY DEVICES CO., LTD Free format text: FORMER OWNER: IRICO GROUP ELECTRONICS CO., LTD. Effective date: 20070727 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20070727 Address after: 621000, No. 35 Mian Xing Dong Road, hi tech Zone, Sichuan, Mianyang Applicant after: Sichuan Sterope Orion Display Co., Ltd. Address before: 712021 No. 1 Rainbow Road, Shaanxi, Xianyang Applicant before: IRICO Group Electronics Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080116 Termination date: 20140113 |