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.