CN103194227A - Method for preparing red long-afterglow luminescent powder - Google Patents
Method for preparing red long-afterglow luminescent powder Download PDFInfo
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- CN103194227A CN103194227A CN2013101094637A CN201310109463A CN103194227A CN 103194227 A CN103194227 A CN 103194227A CN 2013101094637 A CN2013101094637 A CN 2013101094637A CN 201310109463 A CN201310109463 A CN 201310109463A CN 103194227 A CN103194227 A CN 103194227A
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- luminescent powder
- afterglow luminescent
- red long
- powder
- preparation
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Links
- 239000000843 powder Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 32
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000009413 insulation Methods 0.000 claims abstract description 23
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 22
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000001110 calcium chloride Substances 0.000 claims abstract description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 16
- 239000001103 potassium chloride Substances 0.000 claims abstract description 15
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims abstract description 6
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- YNGRGDXYUSSPDK-UHFFFAOYSA-N [S--].[S--].[S--].[Ti+4].[Zn++] Chemical compound [S--].[S--].[S--].[Ti+4].[Zn++] YNGRGDXYUSSPDK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 59
- 238000002360 preparation method Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000005286 illumination Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 238000012856 packing Methods 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000002688 persistence Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a method for preparing red long-afterglow luminescent powder. The method comprises the following steps of: uniformly mixing zinc sulfide, titanium dioxide, aqueous solution of potassium chloride, aqueous solution of potassium permanganate, aqueous solution of europium nitrate, calcium chloride, aqueous solution of indium sulfate and thiourea; putting the mixture into a heating furnace, introducing nitrogen, raising and keeping the temperature, discharging to obtain material blocks at the temperature of 700-800 DEG C after thermal insulation is ended, and cooling; removing non-luminance substances under an ultraviolet lamp, adding ammonia water for standing and soaking, and washing; and screening the dried powder, selecting the particle size according to the power granularity requirement, and obtaining the titanium zinc sulfide red long-afterglow luminescent powder. The luminescent powder is not limited by the excitation light source, the light absorption is rapid, the light absorption time is short, light with the illumination of 1000lx irradiates for 5 minutes, so that saturation can be achieved, and the red long-afterglow luminescent powder has the advantages of long afterglow time, high initial brightness, uniform particles, low production cost, high water resistance, water insolubility, non-toxicity and non-radioactivity, and the red long-afterglow luminescent powder is not blackened when being rubbed with metals.
Description
Technical field
The present invention relates to a kind of preparation method of luminescent powder, specifically, relate to a kind of preparation method of red long-afterglow luminescent powder, belong to the luminescent powder technical field.
Background technology
Luminescent powder has another name called luminescent powder, and the luminescent powder light-storing paint is a kind of long after glow luminous material, is called for short long-afterglow material storage light powder, claims the noctilucent material luminescent material again.Produce textural defect or impurity defect in the lattice of this class material crystal that forms in building-up process and have luminescent properties, caused luminous to be called self-excitation luminous by the material lattice defective, and by impurity defect cause luminous be called activate luminous.
The red long-afterglow luminescent powder has special optical property, and it all is widely used in a lot of fields.Therefore, the various countries researchist is around the design and the synthetic number of research projects of having launched of emitting red light powder.At present, the red long-afterglow luminescent powder that the various countries researchist develops mainly contains: (1) sulfide series refers to that with CaS and SrS be the alkaline earth sulfide of matrix; (2) titanate series refers to BaTiO
3And CaTiO
3Be the matrix alkaline earth titanate; (3) oxide compound series refers to CaO, MgO to be the alkaline-earth oxide series of matrix; (4) oxysulfide series refers to Y
2O
2S, Y
2O
3Deng the oxysulfide that is matrix.But, above-mentioned all kinds of red long-afterglow luminescent powders, because the influence of poor chemical stability, factors such as excitation light source is restricted, time of persistence is short, production cost height, thereby can not be used widely.
Summary of the invention
The problem to be solved in the present invention is at above deficiency, and a kind of preparation method of red long-afterglow luminescent powder is provided, the be not stimulated light source restriction of this method gained luminescent powder, and extinction is fast, time of persistence is long, cost is low, water-tolerant, non-toxic and non-radioactive.
For solving above technology no problem, the technical solution used in the present invention is as follows: a kind of preparation method of red long-afterglow luminescent powder is characterized in that: described preparation method may further comprise the steps:
(1) with 100～200kg zinc sulphide, 15-30kg titanium dioxide, the europium nitrate aqueous solution 50-150mL of potassium permanganate solution 500-1500mL, the 5-15g/L of potassium chloride solution 1000-2000mL, the 120-800g/L of 60-150g/L, 300-1000g calcium chloride, the Indium Sulfate 50-300 mL of 20-100g/L, 3000-8000g thiocarbamide, mixed 12-24 hour, to even;
Repone K wherein, europium nitrate and indium sulfate etc. are because add-on is few, and add in the mode of solution, can be more prone to mix;
(2) with the raw material after mixing in the step (1), put into process furnace, feed nitrogen, be warming up to 1200-2000 ℃, be incubated 2-6 hour, insulation is come out of the stove for 700 ℃-800 ℃ and is obtained expecting piece after finishing, cooling;
(3) the material piece that step (2) is cooled to room temperature takes out, and removes not shiner under the ultraviolet light, and the generation wavelength of purple light is 365nm, only under ultraviolet light, just can find out not shiner, can't see under other light, add the quiet bubble of ammoniacal liquor after 1-3 hour, water cleans 3-5 time;
(4) dry 7-10 hour to dry with powder 100-150 ℃ after step (3) cleaning, the powder that obtains after the oven dry is sieved, can obtain zinc sulphide titanium red long-afterglow luminescent powder according to the granularity requirements selection globule size of powder.
The mean particle size of described zinc sulphide titanium red long-afterglow luminescent powder is 20-35 μ m, and outward appearance is orange red powder.
In the described step (1), be zinc sulphide 200kg; Titanium dioxide 15kg; Concentration is the potassium chloride solution 1500mL of 60g/1000mL; 700g calcium chloride; Concentration is the potassium permanganate solution 1000mL of 600g/1000mL; Concentration is the europium nitrate solution 120mL of 7g/1000mL, thiocarbamide 7000g, and concentration is the In of 80g/1000mL
2(SO
4)
3Solution 180mL.
Mixing time is 24 hours in the described step (1).
The volume of the feeding amount of nitrogen and process furnace is suitable in the described step (2).
Heating temperature is 1200-2000 ℃ in the described step (2), and soaking time is 3 hours.
Add the ammoniacal liquor 800mL/kg of volume fraction 8% in the described step (3) in the per kilogram material piece, soaked 3 hours.
Drying temperature is 140 ℃ in the described step (4), and be 8 hours time of drying.
Powder sieves through 300 orders in the described step (4).
Zinc sulphide in the described step (1) is plasma crystal zinc sulphide powder, and purity is greater than 99.5%; The high-purity plasma crystal zinc sulphide powder that reaches more than 99.5% with purity is base-material, can improve the quality of products, and the rate that reduces the wastage;
Described titanium dioxide is the fluorescence level;
Ammoniacal liquor described in the step (3) is the analytical pure level, and volumetric concentration is 5%～10%, and add-on is per kilogram material piece 500～1000mL.
Among the present invention, first activator is the Eu(europium nitrate), second activator is Mn(potassium permanganate) and the In(indium sulfate), all add with the solution form, can promote that raw material mixes, in addition, Mn(potassium permanganate) and the In(indium sulfate) adding can impel product to form emitting red light, and prolong time of persistence.
The adding of titanium (titanium dioxide) can partly substitute the Zn ion, and forms octahedral structure, thereby makes Mn produce red emission light.
Repone K and calcium chloride are solubility promoter, can impel to produce desulfurization in the zinc sulphide, with the formation luminescence center, and reduce sintering temperature.
The adding of thiocarbamide can produce weakly reducing atmosphere in sintering process, make trivalent europium Eu
3+Be reduced to divalent europium Eu
2+Thereby, form the emitting red light center, reduce the oxidation of zinc sulphide simultaneously, improve the product yield.
The invention has the advantages that: the luminescent powder for preparing by the inventive method light source restriction that is not stimulated, and extinction is fast, absorbing time short, and 1000lx illumination rayed 5min can reach capacity, time of persistence is long, reaches 240min, initial brightness height, reach 1500mcd/ ㎡, uniform particles, D50 is between 20 ~ 35, and production cost is low, water-tolerant, water insoluble, non-toxic and non-radioactive are with advantages such as not blackening of metal friction; Can be widely used in aspects such as all kinds of luminous signboards, finishing material, toy for children, military affairs, be a kind of environmental protection and energy saving product of widespread use.
The present invention is described in detail below in conjunction with embodiment.
Embodiment
Should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in restriction the present invention.
Embodiment 1,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 100kg in the ball mill mixing machine, titanium dioxide 10kg, concentration is the potassium chloride solution 1200mL of 80g/1000mL, 500g calcium chloride, concentration is the potassium permanganate solution 1000mL of 300g/1000mL, concentration is the europium nitrate aqueous solution 100mL of 5g/1000mL, thiocarbamide 5000g, and concentration is the In of 30g/1000mL
2(SO
4)
3Aqueous solution 120mL, batch mixing 20 hours;
⑵ the raw material that mix above-mentioned steps (1) is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1500 ℃ of insulations 4 hours, after insulation finishes, is down to 700 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ take out the material piece that above-mentioned steps (2) is cooled to room temperature, removes not shiner under the ultraviolet light, adds the NH of volume fraction 10% in the per kilogram material piece
4OH solution 10L, quiet bubble after 3 hours again water clean 5 times;
⑷ the luminescent powder after wash above-mentioned steps (3) is put into baking oven, and 120 ℃ are dried by the fire 10 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 2,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 120kg in the ball mill mixing machine; Titanium dioxide 10kg; Concentration is the potassium chloride solution 1800mL of 100g/1000mL; 800g calcium chloride; Concentration is the potassium permanganate solution 1500mL of 500g/1000mL; Concentration is the europium nitrate aqueous solution 80mL of 8g/1000mL, thiocarbamide 4000g, and concentration is the In of 50g/1000mL
2(SO
4)
3Aqueous solution 200mL, batch mixing 15 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1800 ℃ of insulations 5 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 10% in the per kilogram material piece
4OH solution 500mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 150 ℃ are dried by the fire 7 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 3,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 150kg in the ball mill mixing machine; Titanium dioxide 20kg; Concentration is the potassium chloride solution 1800mL of 80g/1000mL; 800g calcium chloride; Concentration is the potassium permanganate solution 1500mL of 500g/1000mL; Concentration is the europium nitrate aqueous solution 100mL of 10g/1000mL, thiocarbamide 3000g, and concentration is the In of 50g/1000mL
2(SO
4)
3Aqueous solution 200mL, batch mixing 18 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1500 ℃ of insulations 5 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 10% in the per kilogram material piece
4OH solution 800mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 130 ℃ are dried by the fire 9 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 4,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 200kg in the ball mill mixing machine; Titanium dioxide 15kg; Concentration is the potassium chloride solution 1500mL of 60g/1000mL; 700g calcium chloride; Concentration is the potassium permanganate solution 1000mL of 600g/1000mL; Concentration is the europium nitrate solution 120mL of 7g/1000mL, thiocarbamide 7000g, and concentration is the In of 80g/1000mL
2(SO
4)
3Solution 180mL, batch mixing 24 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1750 ℃ of insulations 3 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 8% in the per kilogram material piece
4OH solution 800mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 140 ℃ are dried by the fire 8 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 5,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 180kg in the ball mill mixing machine; Titanium dioxide 25kg; Concentration is the potassium chloride solution 2000mL of 120g/1000mL; 900g calcium chloride; Concentration is the potassium permanganate solution 1200mL of 200g/1000mL; Concentration is the europium nitrate solution 120mL of 7g/1000mL, thiocarbamide 8000g, and concentration is the In of 100g/1000mL
2(SO
4)
3Solution 200mL, batch mixing 16 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1750 ℃ of insulations 5 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 6% in the per kilogram material piece
4OH solution 800mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 140 ℃ are dried by the fire 8 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 6,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 140kg in the ball mill mixing machine; Titanium dioxide 30kg; Concentration is the potassium chloride solution 1600mL of 150g/1000mL; 1000g calcium chloride; Concentration is the potassium permanganate solution 1200mL of 800g/1000mL; Concentration is the europium nitrate solution 150mL of 8g/1000mL, thiocarbamide 6000g, and concentration is the In of 60g/1000mL
2(SO
4)
3Solution 250mL, batch mixing 12 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1200 ℃ of insulations 6 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 6% in the per kilogram material piece
4OH solution 1000mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 150 ℃ are dried by the fire 7 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 7,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 130kg in the ball mill mixing machine; Titanium dioxide 20kg; Concentration is the potassium chloride solution 1100mL of 90g/1000mL; 600g calcium chloride; Concentration is the potassium permanganate solution 1200mL of 120g/1000mL; Concentration is the europium nitrate solution 140mL of 6g/1000mL, thiocarbamide 5000g, and concentration is the In of 40g/1000mL
2(SO
4)
3Solution 230mL, batch mixing 16 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1300 ℃ of insulations 6 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 5% in the per kilogram material piece
4OH solution 1000mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 150 ℃ are dried by the fire 8 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 8,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 160kg in the ball mill mixing machine; Titanium dioxide 20kg; Concentration is the potassium chloride solution 1500mL of 130g/1000mL; 400g calcium chloride; Concentration is the potassium permanganate solution 500mL of 120g/1000mL; Concentration is the europium nitrate solution 130mL of 8g/1000mL, thiocarbamide 4000g, and concentration is the In of 40g/1000mL
2(SO
4)
3Solution 80mL, batch mixing 17 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 2000 ℃ of insulations 3 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 8% in the per kilogram material piece
4OH solution 600mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 130 ℃ are dried by the fire 8 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 9,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 180kg in the ball mill mixing machine; Titanium dioxide 18kg; Concentration is the potassium chloride solution 2000mL of 120g/1000mL; 800g calcium chloride; Concentration is the potassium permanganate solution 1000mL of 700g/1000mL; Concentration is the europium nitrate solution 100mL of 8g/1000mL, thiocarbamide 7000g, and concentration is the In of 70g/1000mL
2(SO
4)
3Solution 200mL, batch mixing 15 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1700 ℃ of insulations 3 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 7% in the per kilogram material piece
4OH solution 700mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 140 ℃ are dried by the fire 7 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Embodiment 10,A kind of preparation method of red long-afterglow luminescent powder may further comprise the steps:
⑴ add zinc sulphide 200kg in the ball mill mixing machine; Titanium dioxide 20kg; Concentration is the potassium chloride solution 1800mL of 80g/1000mL; 900g calcium chloride; Concentration is the potassium permanganate solution 1300mL of 400g/1000mL; Concentration is the europium nitrate solution 120mL of 8g/1000mL, thiocarbamide 400g, and concentration is the In of 90g/1000mL
2(SO
4)
3Solution 230mL, batch mixing 16 hours;
⑵ the raw material that mix is packed in the quartz crucible, seals, and puts into High Temperature Furnaces Heating Apparatus, logical N
2Gas is warming up to 1800 ℃ of insulations 3 hours, after insulation finishes, is down to 800 ℃ and comes out of the stove and obtain expecting piece, and stop logical N
2Gas;
⑶ the material piece that will be cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the NH of volume fraction 7% in the per kilogram material piece
4OH solution 7000mL, quiet bubble clean 5 times with pure water after 3 hours again;
⑷ the luminescent powder after wash is put into baking oven, and 130 ℃ are dried by the fire 8 hours to drying, through 300 order net sub-sieves, make finished product after the packing.
Above embodiment products obtained therefrom is irradiation 5 minutes technical indicator such as following table under 25 ℃, the illumination of 1000lx illumination:
In sum, the product that obtains by the inventive method is because of the raw material ratio difference, every technical indicator difference of product, and conceptual data sees the following form:
Product products obtained therefrom of the present invention and other emitting red light powder 5 minutes technical indicator of irradiation under 25 ℃, the illumination of 1000lx illumination is compared as follows table:
Contrast as can be known from every data target of last table, the product that the present invention produces has good stability, the light source that is not stimulated restriction, particle is little and even, advantage such as time of persistence is long, and can combine with green emitting products such as ZnS:Cu, form one of long-afterglow luminescent powder tricolor powder, use more extensive.
Except as otherwise noted, the percentage ratio that adopts among the present invention is weight percentage.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a red long-afterglow luminescent powder, it is characterized in that: described preparation method may further comprise the steps:
(1) with 100～200kg zinc sulphide, 15-30kg titanium dioxide, the Indium Sulfate 50-300 mL of the europium nitrate aqueous solution 50-150mL of potassium permanganate solution 500-1500mL, the 5-15g/L of potassium chloride solution 1000-2000mL, the 120-800g/L of 60-150g/L, 300-1000g calcium chloride, 20-100g/L, the 3000-8000g thiocarbamide, mixed 12-24 hour, to even;
(2) with the raw material after mixing in the step (1), put into process furnace, feed nitrogen, be warming up to 1200-2000 ℃, be incubated 2-6 hour, insulation is come out of the stove for 700 ℃-800 ℃ and is obtained expecting piece after finishing, cooling;
(3) the material piece that step (2) is cooled to room temperature takes out, and removes not shiner under the ultraviolet light, adds the quiet bubble of ammoniacal liquor after 1-3 hour, and water cleans 3-5 time;
(4) dry 7-10 hour to dry with powder 100-150 ℃ after step (3) cleaning, the powder that obtains after the oven dry is sieved, obtain zinc sulphide titanium red long-afterglow luminescent powder.
2. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1 is characterized in that:
The mean particle size of described zinc sulphide titanium red long-afterglow luminescent powder is 20-35 μ m, and outward appearance is orange red powder.
3. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1 is characterized in that: in the step (1), be zinc sulphide 200kg; Titanium dioxide 15kg; Concentration is the potassium chloride solution 1500mL of 60g/1000mL; 700g calcium chloride; Concentration is the potassium permanganate solution 1000mL of 600g/1000mL; Concentration is the europium nitrate solution 120mL of 7g/1000mL, thiocarbamide 7000g, and concentration is the In of 80g/1000mL
2(SO
4)
3Solution 180mL.
4. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1, it is characterized in that: in the step (1), mixing time is 24 hours.
5. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1, it is characterized in that: in the step (2), the feeding amount of nitrogen is suitable with the volume of process furnace.
6. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1, it is characterized in that: in the step (2), Heating temperature is 1200 ℃-2000 ℃, and soaking time is 3 hours.
7. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1 is characterized in that: in the step (3), add the ammoniacal liquor 800mL/kg of volume fraction 8% in the per kilogram material piece, soaked 3 hours.
8. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1, it is characterized in that: in the step (4), drying temperature is 140 ℃, and be 8 hours time of drying.
9. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1, it is characterized in that: in the step (4), powder sieves through 300 orders.
10. the preparation method of a kind of red long-afterglow luminescent powder as claimed in claim 1, it is characterized in that: in the step (1), described zinc sulphide is plasma crystal zinc sulphide powder, and purity is greater than 99.5%;
Described titanium dioxide is the fluorescence level;
Ammoniacal liquor described in the step (3) is the analytical pure level, and volumetric concentration is 5%～10%, and add-on is per kilogram material piece 500～1000mL.
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| CN106467742A (en) * | 2016-08-29 | 2017-03-01 | 潍坊科澜新材料有限公司 | A kind of preparation method of quick response zinc sulfide luminescent powder |
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