CN1128785A

CN1128785A - Blue fluorescent powder for fluorescent lamp with three primary colors

Info

Publication number: CN1128785A
Application number: CN 95101287
Authority: CN
Inventors: 苏勉曾; 林建华; 朴炳镐
Original assignee: Individual
Current assignee: Individual
Priority date: 1995-02-06
Filing date: 1995-02-06
Publication date: 1996-08-14

Abstract

Its chemical composition is calcium-strontiam-barium chlorophosphate activated by europium, which chemical formula is (Sr5-x-y-zCaxBayEuz)(PO4)3Cl.mB2O3.nLi2O. In luminous spectra excited by ultraviolet light or electron beam peak wavelength is 450 nm and half-width is 39-41nm. Light intensity is about 20% higher than that of aluminate type blue phosphor powder made in Japen. Advantages are: good thermal stability, at temp. 700-800 deg.C in air heating for 20 min., luminous intensity is hardly decay.

Description

Blue fluorescent powder for fluorescent lamp with three primary colors

The invention provides a kind of new method for preparing fluorescent material, utilize this method to prepare to be used for the fluorescent material of the look that turns blue of three-color fluorescent lamp, the blue colour fluorescent powder of its certain company of luminous efficiency efficiency ratio Japan is high by 20～30%.Its chemical constitution is europkium-activated calcium chlorophosphate strontium barium, and its chemical formula can be expressed as:

(Sr _5-x-y-zCa _xBa _yEu _z)(PO ₄) ₃Cl·mB ₂O ₃·nLi ₂O

Trichromatic fluorescent light tube footpath is thin, the tube wall load is big, therefore except the light efficiency that requires fluorescent material high and photochromic pure, also require fluorescent material to have the quality of high anti-light decay.The peak wavelength of the luminescent spectrum of blue colour fluorescent powder under ultraviolet ray or electron-beam excitation of the inventive method preparation is～450nm that the halfwidth of bands of a spectrum is 37～41nm.And the peak wavelength of the luminescent spectrum of certain company's aluminate type blue colour fluorescent powder of Japan is 453nm, and the halfwidth of bands of a spectrum is 59nm.Certain company's aluminate type blue colour fluorescent powder of luminous strength ratio Japan of the blue colour fluorescent powder of the inventive method preparation wants high more than 20%.After 20 minutes, its luminous intensity is not decay almost, increases to some extent on the contrary sometimes 700～800 ℃ of calcinations for the blue colour fluorescent powder of the inventive method preparation.

The present invention prepares the method for blue colour fluorescent powder, be to be raw material with Strontium carbonate powder, strontium chloride, barium carbonate, lime carbonate, strontium monophosphate, Secondary ammonium phosphate, with the europium sesquioxide is activator, with boric acid and Quilonum Retard is additive, through ground and mixed evenly after, in weak reduction gas ammonia and 900～1200 ℃ of following calcinations 2～3 hours.Firing product is cooled to room temperature, through pulverizing, wash, filter and drying, promptly obtains above-mentioned blue emitting phophor, and its composition can be used following general formula:

(Sr _5-x-y-zCa _xBa _yEu _z) (PO ₄) ₃ClmB ₂O ₃NLi ₂O is wherein: 0≤x≤0.2,0≤y≤2.2,0.01≤z≤0.4,0≤m≤0.2,0≤n≤0.1, to take all factors into consideration from luminous efficiency and product cost, and be advisable in 0.015≤z≤0.03.

The luminescent spectrum of blue colour fluorescent powder and the mensuration of relative intensity are carried out on the M-850 of Hitachi type spectrophotofluorometer.Excitation light source adopts the monochromatic ray of 254nm wavelength.The luminescent spectrum that records is Eu ²⁺The d-f transition emission of Gao Zi, as shown in Figure 1.Ordinate zou is a relative luminous intensity, and X-coordinate is wavelength (nm).With the peak height at the peak wavelength place of luminescent spectrum relative value as luminous intensity, with Japan certain company's aluminate type blue colour fluorescent powder luminous intensity values as 100, calculate the luminous intensity values of normalized each sample, as shown in table 1, with blue colour fluorescent powder in air and 700～800 ℃ of following calcinations 20 minutes, its luminous intensity is measured in the cooling back, compare with the luminous intensity of the fluorescent material of handling without calcination, the decay of luminescence rate of most samples is very low, and the luminous intensity after some samples process calcination thermal treatments increases on the contrary to some extent.

The present invention has also studied the influence of the add-on of activator europium ion for the blue colour fluorescent powder luminous intensity, as shown in Figure 2, ordinate zou represent relative luminous intensity (with Japan certain company's blue colour fluorescent powder luminous intensity be 100, and normalization method), X-coordinate is represented europium ion Eu ²⁺Content.Solid line among the figure is without heat treated sample, and dotted line is the sample through 700 ℃ of calcinations.Though when the add-on of europium more than 0.13 mole the time, luminous intensity is greatly improved again, and is many because cost strengthens simultaneously, so the add-on of europium still is advisable with 0.015～0.030 mole.The present invention has also studied additive Quilonum Retard add-on for the blue colour fluorescent powder Effect on Performance, and the result is as shown in table 2.

Embodiment:

(1) according to the represented composition of chemical formula of listed No. 1 sample in the table 1, with SrCl ₂6H ₂O, SrCO ₃, Eu ₂O ₃(NH ₄) ₂HPO ₄Deng analyzing pure reagent is initial reactant, the amount of each reactant of weighing exactly, for example: the SrCl of 0.5mol ₂6H ₂The SrCO of O, 4.45mol ₃, 0.05mol Eu ₂O ₃(NH with 3.12mol ₄) ₂HPO ₄Reactant is mixed and abundant the grinding evenly, be placed in the corundum crucible, in weak reducing atmosphere, slowly be warming up to 950～1000 ℃ of calcinations 2 hours.After treating the firing product cooling, with its pulverizing, washing, drying, promptly obtain europium (II) activated blue emitting phophor, its characteristics of luminescence is shown in number one sample in the table 1.

(2) according to the represented chemical constitution of chemical formula of listed the 2nd～No. 11 sample in the table 1, with SrCO ₃, SrHPO ₄Or SrCl ₂, CaCO ₃Or CaHPO ₄, BaCl ₂, Eu ₂O ₃(NH ₄) ₂HPO ₄Be initial reactant, take by weighing the molar weight of each reactant exactly, reactant is mixed and grind evenly, calcination and treating processes through identical with embodiment 1 can make europium (II) activated blue colour fluorescent powder.Their composition can be used following general formula:

(Sr _3.05-zBa _0.15Ca _1.8Eu _z) (PO ₄) ₃Cl is wherein: 0.02≤z≤0.40.Their luminescent spectrum, relative luminous intensity and luminous thermostability are shown in the 2nd～No. 11 sample in the table 1.

(3) according to the represented chemical constitution of chemical formula of listed the 12nd～No. 14 sample in the table 1, with SrCO ₃, SrHPO ₄Or SrCl ₂, CaCO ₃Or CaHPO ₄, BaCl ₂, Eu ₂O ₃(NH ₄) ₂HPO ₄Be initial reactant, take by weighing the molar weight of each reactant exactly, and take by weighing the H of corresponding molar weight ₃BO ₃As additive.Reactant mixed with additive and grind evenly, through with embodiment 1 in identical calcination and treating processes, can make europkium-activated blue colour fluorescent powder.The available following general formula of their composition:

(Sr _3.03Ba _0.15Ca _1.8Eu _0.02) (PO ₄) ₃ClmB ₂O ₃Wherein: their luminescent spectrum of 0.02≤m≤0.16, relative luminous intensity are shown in the 12nd～No. 14 sample in the table 1.

(4) according to the represented chemical constitution of chemical formula of listed the 1st～No. 6 sample in the table 2, take the step identical with embodiment 1, take by weighing various initial reactants and the additive Quilonum Retard identical with the 12nd～No. 14 sample of synthetic table 1, through mix, grind evenly, calcination and processing, make blue emitting phophor, the available following general formula of their composition:

(Sr _3.0Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃ClnLi ₂0.015≤n in the O formula≤0.09.Their relative luminous intensity, luminous thermostability are as shown in table 2.

Table 1 sample is formed luminescent spectrum luminescent spectrum luminous intensity thermal treatment degree luminous intensity numbering peak wavelength half high bandwidth luminous intensity heat fade rate

Nm nm % % %1 (Sr _4.95Eu _0.05) (PO ₄) ₃Cl 449 35 101 103-22 (Sr _3.03Ba _0.15Ca _1.8Eu _0.02) (PO ₄) ₃Cl 449 37 124 124 03 (Sr _3.01Ba _0.15Ca _1.8Eu _0.04) (PO ₄) ₃Cl 449 37 112 102 14 (Sr _2.99Ba _0.15Ca _1.8Eu _0.06) (PO ₄) ₃Cl 449 41 95 92 35 (Sr _2.97Ba _0.15Ca _1.8Eu _0.08) (PO ₄) ₃Cl 449 41 96 96 06 (Sr _2.95Ba _0.15Ca _1.8Eu _0.10) (PO ₄) ₃Cl 449 39 114 133-167 (Sr _2.93Ba _0.15Ca _1.8Eu _0.12) (PO ₄) ₃Cl 449 40 119 140-188 (Sr _2.91Ba _0.15Ca _1.8Eu _0.14) (PO ₄) ₃Cl 449 37 131 133-29 (Sr _2.89Ba _0.15Ca _1.8Eu _0.16) (PO ₄) ₃Cl 449 37 150 117 2210 (Sr _2.85Ba _0.15Ca _1.8Eu _0.20) (PO ₄) ₃Cl 449 38 120 118 111 (Sr _2.65Ba _0.15Ca _1.8Eu _0.40) (PO ₄) ₃Cl 449 37 95 93 212 (Sr _3.03Ba _0.15Ca _1.8Eu _0.02) (PO ₄) ₃Cl0.06B ₂O ₃451 41 102 113-1013 (Sr _3.03Ba _0.15Ca _1.8Eu _0.02) (PO ₄) ₃Cl0.08B ₂O ₃451 39 116 120-314 (Sr _3.03Ba _0.15Ca _1.8Eu _0.02) (PO ₄) ₃Cl0.10B ₂O ₃451 39 120 120 015 certain company's aluminate type blue colour fluorescent powder 453 59 100 94 6 of Japan

Table 2 sample is formed luminescent spectrum luminescent spectrum luminous intensity thermal treatment degree luminous intensity numbering peak wavelength half high bandwidth luminous intensity heat fade rate

Nm nm % % %1 (Sr _3.00Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃Cl0.015Li ₂O 450 39 107 108-12 (Sr _3.00Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃Cl0.030Li ₂O 450 39 113 105 73 (Sr _3.00Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃Cl _0.045Li ₂O 450 38 106 105 14 (Sr _3.00Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃Cl0.060Li ₂O 450 38 108 109 15 (Sr _3.00Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃Cl0.075Li ₂O 450 38 120 110 106 (Sr _3.00Ba _0.15Ca _1.8Eu _0.05) (PO ₄) ₃Cl0.090Li ₂O 450 38 121 126-47 certain company's aluminate type blue colour fluorescent powder 453 59 100 94 6 of Japan

Claims

1. method for preparing the blue colour fluorescent powder that is used for three-color fluorescent lamp, it is characterized in that with Strontium carbonate powder, strontium chloride, barium carbonate, lime carbonate, strontium monophosphate and Yangization Eu be initial reactant, with boric acid and Quilonum Retard is additive, through high temperature solid state reaction, make at the fluorescent material of ultraviolet ray excited emission peak wavelength down for～450nm blue light.It consists of:

(Sr _5-x-y-zCa _xBa _yEu _z) (PO ₄) ₃ClmB ₂O ₃NLi ₂O is wherein: 0≤x≤0.2,0≤y≤2.2,0.01≤z≤0.4,

0≤m≤0.2，0≤n≤0.1

2. the method for the blue colour fluorescent powder of preparation three-color fluorescent lamp as claimed in claim 1 is characterized in that high temperature solid state reaction is in weakly reducing atmosphere and 900～1200 ℃ of calcinations 1～3 hour.