CN1408812A - Borate red fluorescent powder for color plasma plate display and its producing method - Google Patents
Borate red fluorescent powder for color plasma plate display and its producing method Download PDFInfo
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- CN1408812A CN1408812A CN 01141945 CN01141945A CN1408812A CN 1408812 A CN1408812 A CN 1408812A CN 01141945 CN01141945 CN 01141945 CN 01141945 A CN01141945 A CN 01141945A CN 1408812 A CN1408812 A CN 1408812A
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- red fluorescent
- fluorescent powder
- borate
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- color plasma
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- 239000000843 powder Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000001238 wet grinding Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- GWYXTVGANSBRNB-UHFFFAOYSA-N terbium(iii) oxide Chemical compound O=[Tb]O[Tb]=O GWYXTVGANSBRNB-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 5
- 239000004327 boric acid Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 230000004936 stimulating effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 229910052693 Europium Inorganic materials 0.000 description 7
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- NHSQEUIUNPCJHK-UHFFFAOYSA-N B([O-])([O-])[O-].[Eu+3].[Gd+3].[Y+3].B([O-])([O-])[O-].B([O-])([O-])[O-] Chemical compound B([O-])([O-])[O-].[Eu+3].[Gd+3].[Y+3].B([O-])([O-])[O-].B([O-])([O-])[O-] NHSQEUIUNPCJHK-UHFFFAOYSA-N 0.000 description 2
- QFLPBJNIAWVWJE-UHFFFAOYSA-N [O--].[O--].[O--].[Y+3].[Eu+3] Chemical compound [O--].[O--].[O--].[Y+3].[Eu+3] QFLPBJNIAWVWJE-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- AWIMWGGXVCAWEM-UHFFFAOYSA-N europium(3+) gadolinium(3+) oxygen(2-) yttrium(3+) Chemical compound [O-2].[Eu+3].[Gd+3].[Y+3] AWIMWGGXVCAWEM-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UXWKJMWOKLRSLJ-UHFFFAOYSA-K [Eu+3].P(=O)([O-])([O-])[O-].[Y+3].[V+5] Chemical compound [Eu+3].P(=O)([O-])([O-])[O-].[Y+3].[V+5] UXWKJMWOKLRSLJ-UHFFFAOYSA-K 0.000 description 1
- PXMLGXWGOVHNQX-UHFFFAOYSA-N [Y].[Eu] Chemical compound [Y].[Eu] PXMLGXWGOVHNQX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The production process includes producing mixed RE oxide via precipitation process, adding flux and proper amount of boric acid in stoichiometrical value, mixing, roasting in high temperature furnace, grinding wet sieving, wet milling, wet sieving to obtain slurry, washing with hot water, filtering and stoving. The red fluorescent powder of the present invention has simple production process, low cost, high relative brightness in vacuum ultraviolet stimulating condition and high color purity.
Description
Technical field
The present invention relates to a kind of luminescent material and manufacture method thereof of excited by vacuum ultraviolet, the red integral part of the color plasma flat pannel display of saying so more specifically (PDP) in the three primary colors fluorescent powder.
Background technology
Color plasma flat pannel display (PDP) is the fluorescent material of red, blue, the green three kinds of colors of coating in being filled with mixed inert gas discharge electrodes such as Xe or Xe-Ne, the excited by vacuum ultraviolet fluorescent material that produces when utilizing geseous discharge, reach the purpose of display image, fluorescent material is one of critical material that influences color plasma flat pannel display (PDP) performance.Color plasma flat pannel display (PDP) mainly contains yttrium europium oxide, vanadic acid yttrium europium, vanadium yttrium phosphate europium, Yttrium-gadolinium-europium borate etc. with red fluorescence powder.Excite down at 254nm, yttrium europium oxide, yttrium vanadate, alum yttrium phosphate luminous intensity are all than higher, but excite down at vacuum ultraviolet ray (147nm and 172nm), their luminous intensity is just very low, and brightness is higher down and yttrium borate europium gadolinium excites at vacuum ultraviolet ray (147nm and 172nm).Color plasma flat pannel display (PDP) is that luminous intensity is low with the subject matter of red fluorescence powder now, and purity of color is poor, is badly in need of finding a kind of high color purity, the red fluorescence powder that luminous intensity is high.
American documentation literature USP6097146 has reported a kind of novel yttrium europium oxide gadolinium rouge and powder, and its chemical formula is (Y
1-a-bGd
aEu
b)
2O
3, 0≤a≤0.9; 0.01≤b≤0.20 is to use the high-temperature solid phase reaction method synthetic, earlier by (Y
1-a-bGd
aEu
b)
2O
3Take by weighing Y
2O
3, Gd
2O
3, Eu
2O
3, behind the nitric acid dissolve, adding the oxalic acid solution precipitation, 1000 ℃ of pyrolytic decompositions obtain required rare-earth oxide, add fusing assistant, and behind the mixing, 1400 ℃ of high-temperature roastings can obtain yttrium europium oxide gadolinium rouge and powder.The ratio of attempting content by increasing europium and gadolinium improves the brightness and the purity of color of rouge and powder.In the prescription that american documentation literature USP6097146 is provided, the content of europium is than higher, and its mol ratio has reached 0.1～0.2, and the cost of fluorescent material is higher.
American documentation literature USP6042747 a kind of novel borate rouge and powder of also reporting for work, its chemical formula is (Y
1-a-b-cGd
cM
bEu
a) BO
3, wherein, 0.01≤a≤0.1; 0.1≤b≤0.5, c≤0.1, M is one or several among the Mg Ca Sr Ba.Its synthetic method utilization be sol-gel method, presoma just can synthesize borate rouge and powder in down roasting of low temperature (800 ℃～950 ℃).Adopt this method can be at lesser temps and do not add synthetizing phosphor powder under the fusing assistant condition, and when adopting additive method such as solid reaction process, temperature of reaction is more than 1200 ℃, and often need to add fusing assistant, after pyroreaction, also to carry out fragmentation to powder, sieve, last handling processes such as washing are removing the fusing assistant of staying in the fluorescent material, otherwise these materials can influence the luminous intensity of fluorescent material.Adopting another advantage of the method for sol-gel is to make the thinner fluorescent material of granularity, and the granularity of fluorescent material can be controlled in 0.1～2 mu m range.Another characteristics of U.S. Pat P6042747 are to have introduced alkaline-earth metal to mix up in RE(rare earth) borate rouge and powder, purpose is to improve the luminous intensity of fluorescent material, but, introduced alkaline-earth metal and mixed up the luminous intensity that can not improve borate red fluorescent powder effectively according to our test-results.Another main purpose is to utilize the rouge and powder of the synthetic granularity of sol-gel method at 0.1～2 μ m, is beneficial to color plasma flat pannel display (PDP) and is coated with screen.The more complicated but sol-gel method operates, flow process are also dragged longly, and production cost is higher, and production efficiency is low.So the method with sol-gel is not very real impracticable in the production of red borate fluorescent powder, and the brightness of gained fluorescent material is not high yet.
Summary of the invention
The objective of the invention is to realize a kind of borate red fluorescent powder for color plasma plate display and manufacture method thereof, this red fluorescence powder high color purity, luminous intensity height, and manufacture method simple possible, production cost is low.
To achieve these goals, the present invention takes following technical scheme: a kind of borate red fluorescent powder for color plasma plate display of the present invention, chemical formula are (Y
1-x-y-zGd
zM
yEu
x) BO
3, wherein, 0.01≤x≤0.20; 0≤y≤0.02,0.1＜z＜1, and 1-x-y-z＞0, M is one or several among the La Tb Sm..
The manufacture method of a kind of borate red fluorescent powder for color plasma plate display involved in the present invention comprises the steps:
1) presses chemical formula (Y
1-x-y-zGd
zM
yEu
x) BO
3Prepare burden, wherein, 0.01≤x≤0.20; 0≤y≤0.02,0.1＜z＜1, and 1-x-y-z＞0, M is one or several among La, Tb, the Sm.Proportioning according to above-mentioned chemical formula takes by weighing required rare-earth oxide earlier: lanthanum trioxide (La
2O
3), terbium sesquioxide (Tb
4O
7), Samarium trioxide (Sm
2O
3) in one or more, yttrium oxide (Y
2O
3), gadolinium sesquioxide (Gd
2O
3) and europium sesquioxide (Eu
2O
3), be dissolved in nitric acid (HNO
3) or hydrochloric acid (HCl) in, form rare earth metal salt solutions A.Nitric acid (HNO
3) or the concentration of hydrochloric acid (HCl) do not have influence substantially for dissolution process, therefore to nitric acid (HNO
3) and the concentration of hydrochloric acid (HCl) do not limit.
2) preparation oxalic acid solution or carbonate solution, heated solution A is when the temperature that requires (0～80 ℃), constantly stirred solution A slowly adds oxalic acid for preparing or carbonate solution in the solution A, can obtain the oxalate or the carbonate sediment B of rare earth metal.The concentration of oxalic acid solution or carbonate solution does not have influence substantially for precipitation process.Therefore the concentration to oxalic acid solution or carbonate solution does not limit.
3) sediment B is filtered, in baking oven after 90～140 ℃ of oven dry, the oven dry thing is packed into send into pyrolytic decomposition in the high temperature resistance furnace in the high purity aluminium oxide crucible again.Temperature after 0.5～2 hour, can obtain required rare-earth oxide mixture C 800 ℃～1200 ℃ insulations.
4) press chemical formula (Y
1-x-y-zGd
zLa
yEu
x) BO
3, wherein, 0.01≤x≤0.2; 0≤y≤0.02,0≤z≤1, and 1-x-y-z＞0 quantitatively takes by weighing rare-earth oxide mixture C and required boric acid (H
3BO
3), and then add fusing assistant.The add-on of fusing assistant, by weight calculating, be controlled at total stuff amount 0.1～5% between.
5) compound in the previous step is packed in the blender, add the agate ball of an amount of ratio again, wherein compound is heavy: agate ball is heavy=and 1: 0.5～1.5.Abundant mixing, mixing time 12～36 hours can obtain compound D.
6) compound D is packed into put into the high temperature resistance furnace roasting in the high purity aluminium oxide crucible, maturing temperature is controlled at 1100 ℃～1450 ℃, and soaking time is 1～5 hour, can obtain borate rouge and powder E.
7) borate rouge and powder E wet sieving after milling, screen overflow pack into add the deionized water wet-milling in the ball grinder after rewetting sieve, the ball milling time was controlled between 2～10 hours.After screen underflow is used hot water flush away impurity wherein, filter, put into 90～140 ℃ of oven dry of baking oven again, to obtain required borate rouge and powder G.In above-mentioned steps 1) in, described rare-earth oxide purity all requires more than 99.99%, and nitric acid (HNO
3) or hydrochloric acid (HCl) be excessive nitric acid or excessive hydrochloric acid.
In above-mentioned steps 2) in, during with oxalic acid solution or carbonate solution precipitation, in operating process, control reaction conditions, as the solution pH value between 2-4, if pH value not between 2-4, can add rare nitric acid, dilute hydrochloric acid or ammoniacal liquor regulator solution pH value are between 2-4.The temperature of solution is controlled between 0～80 ℃, on the one hand rare earth is precipitated fully, controls sedimentary granularity on the one hand, to control the granularity of final borate red fluorescent powder.
More than the said carbonate solution of when doing co-precipitation, using, refer to a kind of in volatile salt or the ammonium bicarbonate soln.
More than said fusing assistant be meant NH
4Cl, NH
4F, Na
2SO
4, BaF
2, BaCl
22H
2O, K
2SO
4In one or several.The add-on of fusing assistant be controlled at the total stuff amount weight ratio 0.1～5% between.
More than pack into behind the fusing assistant of the stoichiometric boric acid of said adding and certain weight ratio (0.1～5%) in the ball grinder, add an amount of agate ball, ball milling 12～36 hours forms the compound that mixes, during ball milling, the optimum weight ratio of agate ball amount and mixture is 1: 0.8～1.2.The raw material that mixes is packed in the high purity aluminium oxide crucible, places High Temperature Furnaces Heating Apparatus, roasting in air, and optimum calcination temperature is controlled at 1200 ℃～1250 ℃, is incubated after 3 hours naturally cooling in High Temperature Furnaces Heating Apparatus.After roasting product pulverized, sieve with deionized water is wet, screen overflow adds in the ball grinder, can add deionized water and agate ball simultaneously, the roasting material that adds and the weight ratio of agate ball are 1: 0.5～1, the roasting material that adds and the weight ratio of deionized water are 1: 0.5～2, and gained powder slurry is 1: 5 with hot deionized water washing 2～4 times, each product of roasting powder slurry with the ratio of deionized water.Filter the back 110 ℃ of oven dry down.Advantage of the present invention is:
1 adopts high temperature solid-state method synthetic, and manufacturing process is simple, easy handling.
2 borate rouge and powder provided by the present invention, the optimum mole ratio of europium is between 0.03～0.05, so the production cost of this borate red fluorescent powder is lower.
3 borate fluorescent powders of the present invention glow under excited by vacuum ultraviolet, can be used as the red component in the three primary colors fluorescent powder in the color plasma flat pannel display (PDP).
4 in the rare earth oxide coprecipitation process, and the condition of control reaction comprises the temperature of solution and pH value etc., can control the throw out granularity, thereby reach the purpose of medium particle diameter about 3 μ m of the final fluorescent material of control.
Embodiment
Borate red fluorescent powder and manufacture method thereof to excited by vacuum ultraviolet of the present invention is further described by the following examples, will help product of the present invention and manufacture method are done further to understand.Protection scope of the present invention is not subjected to the restriction of these embodiment, and protection scope of the present invention is determined by claims.
Implement Comparative Examples:
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of present embodiment is (Y
0.86Gd
0.10Eu
0.04) BO
3, wherein, x=0.04, y=0, z=0.10.Its manufacture method is, take by weighing required stoichiometric rare earth oxide, with weight percent concentration is 40% nitric acid dissolve, more excessive 10% than Theoretical Calculation amount, and then is 20% oxalic acid solution precipitation with weight percent concentration, than Theoretical Calculation amount excessive 30%, make precipitation fully, obtain throw out, the high purity aluminium oxide crucible of packing into after the oven dry, 900 ℃ of pyrolytic decompositions obtain rare earth oxide mixture A.
In mixture A, add required stoichiometric boric acid and weight ratio again and be 0.2% fusing assistant, and then with they mixings in the ball grinder of packing into.
The raw material that mixes is packed in the high purity aluminium oxide crucible, places High Temperature Furnaces Heating Apparatus, roasting in air, and maturing temperature is controlled at 1230 ℃, is incubated after 3 hours naturally cooling in High Temperature Furnaces Heating Apparatus.After roasting product pulverized, sieve with deionized water is wet, screen overflow adds in the ball grinder, add deionized water and agate ball simultaneously, the roasting material that adds and the weight ratio of agate ball are 1: 1, the weight ratio with the roasting product deionized water that adds is 1: 2, and gained powder slurry is 1: 5 with hot deionized water washing 2～4 times, each product of roasting powder slurry with the ratio of deionized water.Filter the back 110 ℃ of oven dry down.
Embodiment 1～4
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 1 is (Y
0.654Gd
0.300La
0.006Eu
0.040) BO
3, wherein, x=0.040, y=0.006, z=0.300, M are La.Manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 2 is (Y
0.654Gd
0.300Tb
0.006Eu
0.040) BO
3, wherein, x=0.040, y=0.006, z=0.300, M are Tb.Manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 3 is (Y
0.654Gd
0.300Sm
0.006Eu
0.040) BO
3, wherein, x=0.040, y=0.006, z=0.300, M are Sm.Manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 4 is (Y
0.650Gd
0.300Tb
0.008Eu
0.042) BO
3, wherein, x=0.042, y=0.008, z=0.030, M are Tb.Manufacture method is identical with the enforcement Comparative Examples.
By test result as can be seen, embodiment 1～4 is vacuum ultraviolet-excited following, and color ratio is suitable with the enforcement Comparative Examples, and luminous intensity is all compared than embodiment height.Especially embodiment 4, reached 106, exceed 6%.The luminescent properties contrast of embodiment 1～4 sees the following form 1:
Table 1 luminescent properties contrast table
| Sequence number | Chemical formula | Chromaticity coordinates | Color ratio | Relative brightness | |||
| ????x | ????y | ????R | ????G | ????B | |||
| Implement Comparative Examples | (Y 0.86Gd 0.10Eu 0.040)BO 3 | ????0.635 | ????0.355 | ????98 | ????1 | ????1 | ????100 |
| Embodiment 1 | (Y 0.654Gd 0.300La 0.006Eu 0.040)BO 3 | ????0.641 | ????0.355 | ????98 | ????1 | ????1 | ????104 |
| Embodiment 2 | (Y 0.654Gd 0.300Tb 0.006Eu 0.040)BO 3 | ????0.647 | ????0.351 | ????98 | ????1 | ????1 | ????102 |
| Embodiment 3 | (Y 0.654Gd 0.300Sm 0.006Eu 0.040)BO 3 | ????0.636 | ????0.353 | ????98 | ????1 | ????1 | ????101 |
| Embodiment 4 | (Y 0.650Gd 0.300Tb 0.008Eu 0.042)BO 3 | ????0.640 | ????0.355 | ????98 | ????1 | ????1 | ????106 |
Annotate: above data are to excite test gained down at vacuum ultraviolet ray (147nm and 172nm)
Embodiment 5～9
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 5 is (Y
0.754Gd
0.200Tb
0.006Eu
0.04) BO
3, M is Tb, manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 6 is (Y
0.554Gd
0.402Tb
0.004Eu
0.04) BO
3, M is Tb, manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 7 is (Y
0.354Gd
0.598Tb
0.008Eu
0.04) BO
3, M is Tb, manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 8 is (Y
0.154Gd
0.792Tb
0.014Eu
0.04) BO
3, M is Tb, manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 9 is (Y
0.200Gd
0.754Tb
0.006Eu
0.04) BO
3, M is Tb, manufacture method is identical with the enforcement Comparative Examples.
By test result as can be seen, the color ratio of embodiment 5～9 is suitable with the enforcement Comparative Examples, and relative brightness is compared with implementing Comparative Examples, is greatly improved.
The luminescent properties contrast of embodiment 5～9 sees the following form 2:
Table 2 luminescent properties contrast table
| Sequence number | Chemical formula | Chromaticity coordinates | Color ratio | Relative brightness | |||
| ????x | ????y | ????R | ????G | ????B | |||
| Implement Comparative Examples | (Y 0.86Gd 0.10Eu 0.040)BO 3 | ????0.635 | ????0.355 | ????98 | ????1 | ????1 | ????100 |
| Embodiment 5 | (Y 0.754Gd 0.200Tb 0.006Eu 0.04)BO 3 | ????0.632 | ????0.355 | ????98 | ????1 | ????1 | ????106 |
| Embodiment 6 | (Y 0.554Gd 0.402Tb 0.004Eu 0.04)BO 3 | ????0.637 | ????0.355 | ????98 | ????1 | ????1 | ????101 |
| Embodiment 7 | (Y 0.354Gd 0.598Tb 0.008Eu 0.04)BO 3 | ????0.638 | ????0.355 | ????98 | ????1 | ????1 | ????111 |
| Embodiment 8 | (Y 0.154Gd 0.792Tb 0.014Eu 0.04)BO 3 | ????0.637 | ????0.353 | ????98 | ????1 | ????1 | ????101 |
| Embodiment 9 | (Y 0.200Gd 0.754Tb 0.006Eu 0.04)BO 3 | ????0.636 | ????0.355 | ????98 | ????1 | ????1 | ????104 |
Annotate: above data are to excite test gained down at vacuum ultraviolet ray (147nm and 172nm)
Embodiment 10～12
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 10 is (Y
0.478Gd
0.50La
0.006Eu
0.016) BO
3, wherein, x=0.016, y=0.006, z=0.50, M are La.Manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 11 is (Y
0.462Gd
0.50La
0.006Eu
0.032) BO
3, wherein, x=0.032, y=0.006, z=0.50, M are La.Manufacture method is identical with the enforcement Comparative Examples.
The chemical formula of the borate red fluorescent powder product of the excited by vacuum ultraviolet of embodiment 12 is (Y
0.446Gd
0.50La
0.006Eu
0.048) BO
3, wherein, x=0.048, y=0.006, z=0.50, M are La.Manufacture method is identical with the enforcement Comparative Examples.
By the test result of embodiment 10～12 as can be seen, all be 0.04 o'clock at europium content, the brightness of embodiment 12 is greatly improved.Along with the increase of europium content, the brightness of fluorescent material progressively improves, but the price of europium is higher, takes all factors into consideration, and it is relatively good to add mol ratio and be about 0.05 europium.
The luminescent properties contrast of embodiment 10～12 sees the following form 3:
Table 3 luminescent properties contrast table
| Sequence number | Chemical formula | Chromaticity coordinates | Color ratio | Relative brightness | |||
| ????x | ????y | ????R | ????G | ????B | |||
| Implement Comparative Examples | ????(Y 0.86Gd 0.020Eu 0.040)BO 3 | ????0.638 | ????0.358 | ????98 | ????1 | ????1 | ????100 |
| Embodiment 10 | ????(Y 0.478Gd 0.50La 0.006Eu 0.016)BO 3 | ????O?625 | ????O.350 | ????96 | ????1 | ????3 | ????86 |
| Embodiment 11 | ????(Y 0.462Gd 0.50La 0.006Eu 0.032)BO 3 | ????0.630 | ????O.356 | ????97 | ????1 | ????2 | ????105 |
| Embodiment 12 | ????(Y 0.446Gd 0.50La 0.006Eu 0.048)BO 3 | ????O.654 | ????0.344 | ????98 | ????1 | ????1 | ????112 |
Annotate: above data are to excite test gained down at vacuum ultraviolet ray (147nm and 172nm)
Claims (8)
1. borate red fluorescent powder for color plasma plate display, it is characterized in that: the chemical formula of this fluorescent material is (Y
1-x-y-zGd
zM
yEu
x) BO
3, wherein, 0.01≤x≤0.20; 0≤y≤0.02,0.1＜z＜1, and 1-x-y-z＞0, M is one or several among La, Tb, the Sm..
2. a manufacture method of making the described borate red fluorescent powder for color plasma plate display of claim 1 is characterized in that this method comprises the steps:
1) presses chemical formula (Y
1-x-y-zGd
zM
yEu
x) BO
3Prepare burden, wherein, 0.01≤x≤0.20; 0≤y≤0.02,0.1＜z＜1, and 1-x-y-z＞0, M is one or several among La, Tb, the Sm, the proportioning according to above-mentioned chemical formula takes by weighing required rare-earth oxide earlier: lanthanum trioxide (La
2O
3), terbium sesquioxide (Tb
4O
7), Samarium trioxide (Sm
2O
3) in one or more, yttrium oxide (Y
2O
3), gadolinium sesquioxide (Gd
2O
3) and europium sesquioxide (Eu
2O
3), be dissolved in nitric acid (HNO
3) or hydrochloric acid (HCl) in, form rare earth metal salt solutions A;
2) preparation oxalic acid solution or carbonate solution, heated solution A are during to 0～80 ℃ of institute's temperature that requires, and constantly stirred solution A slowly adds oxalic acid for preparing or carbonate solution in the solution A, obtains the oxalate or the carbonate sediment B of rare earth metal;
3) sediment B is filtered, 90～140 ℃ of oven dry in baking oven are packed the oven dry thing into and are sent into pyrolytic decomposition in the high temperature resistance furnace, 800 ℃～1200 ℃ of decomposition temperatures in the high purity aluminium oxide crucible, be incubated after 0.5～2 hour, can obtain required rare-earth oxide mixture C;
4) press chemical formula (Y
1-x-y-zGd
zLa
yEu
x) BO
3, wherein, 0.01≤x≤0.20; 0≤y≤0.02,0.1＜z＜1, and 1-x-y-z＞0 quantitatively takes by weighing rare-earth oxide mixture C and boric acid (H
3BO
3), and then add fusing assistant, the add-on of fusing assistant, by weight calculating, be controlled at total stuff amount 0.1～5% between;
5) compound in the previous step is put into blender, add agate ball again, fully mixing can obtain compound D;
6) compound D is packed into put into the high temperature resistance furnace roasting in the high purity aluminium oxide crucible, maturing temperature is controlled at 1100 ℃～1450 ℃, and soaking time is 1～5 hour, can obtain borate rouge and powder E;
7) wet sieving after borate rouge and powder E pulverizes, screen overflow pack into add the deionized water wet-milling in the ball grinder after rewetting sieve, the ball milling time was controlled between 2～10 hours, after screen underflow is used hot water flush away impurity wherein, filter, 90～140 ℃ of oven dry of baking oven are put in washing again, obtain required boron to salt rouge and powder G.
3. manufacturing borate red fluorescent powder for color plasma plate display according to claim 2 is characterized in that: in above-mentioned steps 1) in, described rare-earth oxide purity all requires more than 99.99%, and nitric acid (HNO
3) or hydrochloric acid (HCl) be excessive nitric acid or excessive hydrochloric acid.
4. manufacturing borate red fluorescent powder for color plasma plate display according to claim 2 is characterized in that: in above-mentioned steps 2) in, described carbonate solution is volatile salt or ammonium bicarbonate soln.
5. manufacturing borate red fluorescent powder for color plasma plate display according to claim 2 is characterized in that: in above-mentioned steps 2) in, during with oxalic acid solution or carbonate solution precipitation, the pH value of regulator solution is between 2-4.
6. manufacturing borate red fluorescent powder for color plasma plate display according to claim 2 is characterized in that: in above-mentioned steps 2) in, during with oxalic acid solution or carbonate solution precipitation, the temperature of solution is controlled between 0～80 ℃.
7. manufacturing borate red fluorescent powder for color plasma plate display according to claim 2 is characterized in that: in above-mentioned steps 4) in, described fusing assistant comprises NH
4Cl, NH
4F, Na
2SO
4, BaF
2, BaCl
22H
2O, K
2SO
4In one or several, and the add-on of fusing assistant be controlled at total stuff amount 0.1～2% between.
8. manufacturing borate red fluorescent powder for color plasma plate display according to claim 2, it is characterized in that: in above-mentioned steps 5) in, add agate ball during described batch mixing, its ratio control is heavy at compound: agate ball is heavy=and 1: 0.5～1.5, mixing time 12-36 hour.
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300281C (en) * | 2004-12-08 | 2007-02-14 | 中国科学院长春应用化学研究所 | Vacuum ultraviolet excited rare-earth borovanadate system red fluorescent powder and preparing method |
| CN100372912C (en) * | 2005-07-01 | 2008-03-05 | 中山大学 | A kind of rare earth red luminescent material for PDP and preparation method thereof |
| CN101260299B (en) * | 2008-04-03 | 2010-06-02 | 沈阳化工学院 | A method for preparing yttrium oxide, gadolinium, europium nano-luminescent powder by microemulsion method |
| CN102277169A (en) * | 2011-01-30 | 2011-12-14 | 杨凌冠阳农业科技有限公司 | Light conversion agent for agricultural film, preparation method thereof, application thereof and method for manufacturing agricultural film |
| CN102517013A (en) * | 2011-11-24 | 2012-06-27 | 合肥工业大学 | Photon conversion material and preparation method thereof |
| CN102766457A (en) * | 2012-06-29 | 2012-11-07 | 彩虹集团电子股份有限公司 | Preparation method for yttrium gadolinium europium oxide red fluorescent powder applicable to 3D PDP |
| CN107858146A (en) * | 2017-09-30 | 2018-03-30 | 西安建筑科技大学 | A kind of Eu3+Ion doping borate（K6Ba4B8O19）The synthetic method of base red fluorescent powder |
-
2001
- 2001-09-25 CN CN 01141945 patent/CN1210371C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300281C (en) * | 2004-12-08 | 2007-02-14 | 中国科学院长春应用化学研究所 | Vacuum ultraviolet excited rare-earth borovanadate system red fluorescent powder and preparing method |
| CN100372912C (en) * | 2005-07-01 | 2008-03-05 | 中山大学 | A kind of rare earth red luminescent material for PDP and preparation method thereof |
| CN101260299B (en) * | 2008-04-03 | 2010-06-02 | 沈阳化工学院 | A method for preparing yttrium oxide, gadolinium, europium nano-luminescent powder by microemulsion method |
| CN102277169A (en) * | 2011-01-30 | 2011-12-14 | 杨凌冠阳农业科技有限公司 | Light conversion agent for agricultural film, preparation method thereof, application thereof and method for manufacturing agricultural film |
| CN102517013A (en) * | 2011-11-24 | 2012-06-27 | 合肥工业大学 | Photon conversion material and preparation method thereof |
| CN102517013B (en) * | 2011-11-24 | 2014-12-03 | 合肥工业大学 | Photon conversion material and preparation method thereof |
| CN102766457A (en) * | 2012-06-29 | 2012-11-07 | 彩虹集团电子股份有限公司 | Preparation method for yttrium gadolinium europium oxide red fluorescent powder applicable to 3D PDP |
| CN107858146A (en) * | 2017-09-30 | 2018-03-30 | 西安建筑科技大学 | A kind of Eu3+Ion doping borate（K6Ba4B8O19）The synthetic method of base red fluorescent powder |
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| Publication number | Publication date |
|---|---|
| CN1210371C (en) | 2005-07-13 |
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