CN103468255B - Chlorine borate luminescent material and preparation method thereof - Google Patents
Chlorine borate luminescent material and preparation method thereof Download PDFInfo
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- CN103468255B CN103468255B CN201310443892.8A CN201310443892A CN103468255B CN 103468255 B CN103468255 B CN 103468255B CN 201310443892 A CN201310443892 A CN 201310443892A CN 103468255 B CN103468255 B CN 103468255B
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- HITBOAGYESUOFH-UHFFFAOYSA-N boric acid hydrochloride Chemical compound Cl.OB(O)O HITBOAGYESUOFH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 61
- 239000011777 magnesium Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- -1 europium ion Chemical class 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001940 europium oxide Inorganic materials 0.000 claims description 5
- 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 5
- 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 description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 235000014692 zinc oxide Nutrition 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000009841 combustion method Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000009877 rendering Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 9
- 238000012544 monitoring process Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910019427 Mg(NO3)2-6H2O Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The invention discloses a chlorine borate luminescent material and a preparation method thereof. The luminescent material employs Eu<2+> as an activation ion and has a chemical general formula of M3-3xEu3xB7O13Cl, wherein M is one of Mg<2+> and Zn<2+>, 0.001<=x<=0.25, and the luminescent material is synthesized by high-temperature solid-phase roasting. The prepared rare earth luminescent material emits blue light under the excitation of ultraviolet light, has good luminescent intensity, stability and color-rendering performance, and is applicable to near ultraviolet type white light LED devices. The preparation of the matrix material is simple, the product is easy to collect, no waste water and gas are discharged, and the preparation method is environment-friendly and especially suitable for continuous production, and the prepared chlorine borate luminescent material has stable physical properties and chemical properties.
Description
Technical field
The present invention relates to a kind of rareearth blue fluorescent material, particularly a kind of Chlorine borate luminescent material and preparation method thereof.
Background technology
Rareearth blue fluorescent material can extensive use and many fields, such as display, lighting device, coating, light altering film for agriculture, send the anti-counterfeiting mark etc. of blue-fluorescence.In rare-earth luminescent material, usual rare-earth europium is as fluorescence-activation source, and the transition of positive divalent europium can produce blue-fluorescence, and the transition of positive trivalent europium ion produces red fluorescence.Because europium ion can only exist with the form stable of positive trivalent in atmosphere, this just makes the rareearth blue fluorescent material that preparation stability is high comparatively difficult.
Along with the development of near ultraviolet-ultraviolet light (350 ~ 410nm) LED chip, be suitable for the focus that fluorescent material with three basic colour that InGaN (350 ~ 410nm) tube core excites becomes people's research.But, develop that to be suitable for the LED blue fluorescent material system that InGaN (350 ~ 410nm) tube core excites actually rare.Even if successfully develop LED blue fluorescent material system, because luminous efficiency is low or poor chemical stability, it is caused to differ greatly from practical application.Therefore, need at present a kind of luminous efficiency high and the novel blue fluorescent material that chemical stability is excellent.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, that a kind of high brightness is provided, that chemical stability is excellent novel blue light fluorescent material and preparation method thereof.
For reaching above object, the technical solution used in the present invention is to provide a kind of Chlorine borate luminescent material, and it is with Eu
2+for active ions, chemical general formula is M
3-3xeu
3xb
7o
13cl, wherein, M is Mg
2+, Zn
2+in one, 0.001≤x≤0.25.
The preparation method of a kind of Chlorine borate luminescent material as above, adopt high temperature solid-phase sintering synthesis, concrete steps are as follows:
1, with the compound containing M ion, containing europium ion Eu
3+compound, containing boron ion B
3+compound, containing chloride ion Cl
-compound be raw material, by chemical general formula M
3-3xeu
3xb
7o
13cl takes each raw material, and wherein, 0.001≤x≤0.25, M is magnesium ion Mg
2+, zinc ion Zn
2+in one; Mix after the raw material taken is ground respectively;
2, mixture step 1 obtained is first time calcining in air atmosphere, and calcining heat is 300 ~ 600 DEG C, and calcination time is 1 ~ 10 hour;
3, mixture step 2 obtained second time calcining in air atmosphere, calcining heat is 600 ~ 800 DEG C, and calcination time is 1 ~ 10 hour;
4, after naturally cooling, grind and mix, under reducing atmosphere third firing, calcining heat is 800 ~ 1000 DEG C, and calcination time is 1 ~ 10 hour, obtains a kind of Chlorine borate luminescent material.
In above-mentioned preparation method, reducing atmosphere for be obtained by activated carbon powder, carbon black combustion method, or is nitrogen/hydrogen mixed gas.First time, the temperature of calcining was 350 ~ 600 DEG C, and calcination time is 3 ~ 8 hours.The temperature of second time calcining is 620 ~ 750 DEG C, and calcination time is 3 ~ 8 hours.The temperature of calcining under reducing atmosphere is 800 ~ 950 DEG C, and calcination time is 3 ~ 10 hours.
In technical solution of the present invention, M is magnesium ion Mg
2+compound be one in magnesium oxide, basic magnesium carbonate, magnesium chloride, magnesium hydroxide, magnesium nitrate or any two kinds; M is zinc ion Zn
2+compound be one in zinc oxide, zinc carbonate, zinc chloride, zinc hydroxide, zinc nitrate or any two kinds.Containing europium ion Eu
3+compound be one in europium oxide, europium nitrate.Containing boron ion B
3+compound be one in boron oxide, boric acid.
Compared with prior art, the present invention has following beneficial effect:
1, Chlorine borate matrix provided by the invention, is easy to realize the filling of bivalent rare earth europium ion in this matrix, and rare-earth cation can stable existence in matrix.
2, fluorescent material provided by the invention can be excited by near ultraviolet light well, has good luminous intensity, stability and color rendering, can be applicable near ultraviolet type white light LED part, prepares high-power LED.
3, the preparation process of host material of the present invention is simple, product easily collecting, without the discharge of waste water gas, and environmental friendliness, especially applicable continuous prodution thus prepare the fluorescent material of physical property and stable chemical nature.
Accompanying drawing explanation
The Mg of Fig. 1 obtained by the embodiment of the present invention 1
2.85eu
0.15b
7o
13the X-ray powder diffraction pattern of Cl material sample;
The Mg of Fig. 2 obtained by the embodiment of the present invention 1
2.85eu
0.15b
7o
13the exciting light spectrogram of Cl material sample under monitoring wavelength 421 nanometer;
The Mg of Fig. 3 obtained by the embodiment of the present invention 1
2.85eu
0.15b
7o
13the luminescent spectrum figure of Cl material sample under 330 nano wave lengths excite;
The Mg of Fig. 4 obtained by the embodiment of the present invention 3
2.997eu
0.003b
7o
13the exciting light spectrogram of Cl material sample under monitoring wavelength 425 nanometer;
The Mg of Fig. 5 obtained by the embodiment of the present invention 3
2.997eu
0.003b
7o
13the luminescent spectrum figure of Cl material sample under 398 nano wave lengths excite;
The Zn of Fig. 6 obtained by the embodiment of the present invention 4
2.85eu
0.15b
7o
13the X-ray powder diffraction pattern of Cl material sample;
The Zn of Fig. 7 obtained by the embodiment of the present invention 4
2.85eu
0.15b
7o
13the exciting light spectrogram of Cl material sample under monitoring wavelength 432 nanometer;
The Zn of Fig. 8 obtained by the embodiment of the present invention 4
2.85eu
0.15b
7o
13the luminescent spectrum figure of Cl material sample under 330 nano wave lengths excite;
The Zn of Fig. 9 obtained by example 4 of the present invention
2.85eu
0.15b
7o
13cl material sample is monitoring wavelength 440, the decay spectrogram under excitation wavelength 266 nanometer.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1:
Preparation Mg
2.85eu
0.15b
7o
13cl
According to chemical formula Mg
2.85eu
0.15b
7o
13cl takes raw material respectively, magnesium chloride Mg Cl
2-6H
2o:0.677 gram, magnesium oxide MgO:0.631 gram, boric acid H
3bO
3: 2.885 grams, europium oxide Eu
2o
3: 0.176 gram, to grind and after mixing in agate mortar, first time presintering in air atmosphere, pre-sintering temperature 350 DEG C, sintering time 5 hours, is cooled to room temperature, takes out sample; Be placed in Muffle furnace after it again fully being ground, second time calcining in air atmosphere, calcining heat is 750 DEG C, and calcination time is 6 hours, is cooled to room temperature, takes out sample; Be placed in atmosphere furnace after it again fully being ground, (be embedded in activated carbon powder) calcining under reducing atmosphere, calcining heat is 900 DEG C, and calcination time is 8 hours, namely obtains powder shaped chlorate luminescent material.
See accompanying drawing 1, it is the X-ray powder diffraction pattern preparing sample by the present embodiment technical scheme, and XRD test result shows, prepared Mg
2.85eu
0.15b
7o
13cl is monophase materials, and the impurity thing without any other exists mutually, and degree of crystallinity is better.
See accompanying drawing 2, it is the exciting light spectrogram that sample prepared by the present embodiment obtains under 421 nanometer monitorings; As can be seen from the figure, can being effectively excited in 250 ~ 400 nanometers of this material, can mate the White-light LED chip of ultraviolet excitation well.
See accompanying drawing 3, it is the luminescent spectrum figure that sample prepared by the present embodiment obtains under 330 nano wave lengths excite; This phosphor emission wavelength is based on 450 nanometers.Calculated by CIE, learn that its coordinate is x=0.1802, y=0.0779, also just in time drop on blue region, it can be applicable to the white light LEDs that black light is excitation source very well.
Embodiment 2:
Preparation Mg
2.7eu
0.3b
7o
13cl
According to chemical formula Mg
2.7eu
0.3b
7o
13cl takes raw material respectively, magnesium chloride Mg Cl
2-6H
2o:0.677 gram, basic magnesium carbonate 3MgCO
3mg (OH)
23H
2o:1.315 gram, boron oxide B
2o
3: 1.625 grams, europium oxide Eu
2o
3: 0.352 gram, to grind and after mixing in agate mortar, first time presintering in air atmosphere, pre-sintering temperature 400 DEG C, sintering time 4 hours, is cooled to room temperature, takes out sample; Be placed in Muffle furnace after it again fully being ground, second time calcining in air atmosphere, calcining heat is 650 DEG C, and calcination time is 7 hours, is cooled to room temperature, takes out sample; Be placed in atmosphere furnace after it again fully being ground, (be embedded in carbon black) calcining under reducing atmosphere, calcining heat is 950 DEG C, and calcination time is 7 hours, namely obtains powder shaped chlorate luminescent material.Its main structural behaviour, excitation spectrum are similar to embodiment 1 with luminescent spectrum.
Embodiment 3:
Preparation Mg
2.997eu
0.003b
7o
13cl
According to chemical formula Mg
2.997eu
0.003b
7o
13cl, takes respectively: magnesium chloride Mg Cl
2-6H
2o:0.677 gram, magnesium nitrate Mg (NO
3)
2-6H
2o:5.123 gram, boron oxide B
2o
3: 1.625 grams, europium nitrate Eu (NO
3)
3-6 H
2o:0.009 gram, grinds and after mixing in agate mortar, first time presintering in air atmosphere, pre-sintering temperature 450 DEG C, and sintering time 4 hours, is cooled to room temperature, takes out sample; Be placed in Muffle furnace after it again fully being ground, second time calcining in air atmosphere, calcining heat is 700 DEG C, and calcination time is 5 hours, is cooled to room temperature, takes out sample; Be placed in atmosphere furnace after it again fully being ground, calcine in the atmosphere furnace being connected with nitrogen/hydrogen mixed gas, calcining heat is 850 DEG C, and calcination time is 10 hours, namely obtains powder shaped chlorate luminescent material.
See accompanying drawing 4, it is the exciting light spectrogram that sample prepared by the present embodiment obtains under 425 nanometer monitorings; As can be seen from the figure, can being effectively excited in 250 ~ 400 nanometers of this material, can mate the White-light LED chip of ultraviolet excitation well.
See accompanying drawing 5, it is the luminescent spectrum figure that sample prepared by the present embodiment obtains under 330 nano wave lengths excite; This phosphor emission wavelength is based on 450 nanometers.Calculated by CIE simultaneously, learn that its coordinate is x=0.160, y=0.039, also just in time drop on blue region, it can be applicable to the white light LEDs that black light is excitation source very well.
Embodiment 4:
Preparation Zn
2.85eu
0.15b
7o
13cl
According to chemical formula Zn
2.85eu
0.15b
7o
13cl, takes respectively: zinc chloride ZnCl
2-6H
2o:0.454 gram, zinc oxide ZnO:1.275 gram, boric acid H
3bO
3: 2.885 grams, europium nitrate Eu (NO
3)
3-6H
2o:0.176 gram, grinds and after mixing in agate mortar, first time presintering in air atmosphere, pre-sintering temperature 450 DEG C, and sintering time 4 hours, is cooled to room temperature, takes out sample; Be placed in Muffle furnace after it again fully being ground, second time calcining in air atmosphere, calcining heat is 700 DEG C, and calcination time is 5 hours, is cooled to room temperature, takes out sample; Be placed in atmosphere furnace after it again fully being ground, (be embedded in carbon dust) calcining under reducing atmosphere, calcining heat is 800 DEG C, and calcination time is 10 hours, namely obtains powder shaped chlorate luminescent material.
See accompanying drawing 6, it is the X-ray powder diffraction pattern preparing sample by the present embodiment technical scheme, and XRD test result shows, prepared Zn
2.85eu
0.15b
7o
13cl is monophase materials, and the impurity thing without any other exists mutually, and degree of crystallinity is better.
See accompanying drawing 7, it is the exciting light spectrogram that sample prepared by the present embodiment obtains under 432 nanometer monitorings; As can be seen from the figure, this material can effectively be excited in 250 ~ 400 nanometers, can mate the White-light LED chip of ultraviolet excitation well.
See accompanying drawing 8, it is the luminescent spectrum figure that sample prepared by the present embodiment obtains under 330 nano wave lengths excite; This phosphor emission wavelength is based on 450 nanometers.Calculated by CIE simultaneously, learn that its coordinate is x=0.174, y=0.117, also just in time drop on blue region, it can be applicable to the white light LEDs that black light is excitation source very well.
See accompanying drawing 9, it is that sample prepared by the present embodiment is monitoring wavelength 440 nanometer, the decay spectrogram under excitation wavelength 266 nanometer.It was 611 nanoseconds by calculating the fluorescence lifetime of this embodiment.
Embodiment 5:
Preparation Zn
2.4eu
0.6b
7o
13cl
According to chemical formula Zn
2.4eu
0.6b
7o
13cl, takes respectively: zinc chloride ZnCl
2-6H
2o:0.454 gram, zinc nitrate Zn (NO
3)
2-6 H
2o:3.570 gram, boric acid H
3bO
3: 2.885 grams, europium nitrate Eu (NO
3)
3-6 H
2o:1.784 gram, grinds and after mixing in agate mortar, first time presintering in air atmosphere, pre-sintering temperature 450 DEG C, and sintering time 4 hours, is cooled to room temperature, takes out sample; Be placed in Muffle furnace after it again fully being ground, second time calcining in air atmosphere, calcining heat is 700 DEG C, and calcination time is 5 hours, is cooled to room temperature, takes out sample; Be placed in atmosphere furnace after it again fully being ground, calcine in the atmosphere furnace being connected with nitrogen/hydrogen mixed gas, calcining heat is 850 DEG C, and calcination time is 10 hours, namely obtains powder shaped chlorate luminescent material.Its main structural behaviour, excitation spectrum are similar to embodiment 4 with luminescent spectrum.
Embodiment 6:
Preparation Zn
2.25eu
0.75b
7o
13cl
According to chemical formula Zn
2.25eu
0.75b
7o
13cl, takes respectively: zinc chloride ZnCl
2-6H
2o:0.454 gram, zinc carbonate ZnCO
3: 1.8813 grams, boron oxide B
2o
3: 1.625 grams, europium oxide Eu
2o
3: 0.879 gram, to grind and after mixing in agate mortar, first time presintering in air atmosphere, pre-sintering temperature 450 DEG C, sintering time 4 hours, is cooled to room temperature, takes out sample; Be placed in Muffle furnace after it again fully being ground, second time calcining in air atmosphere, calcining heat is 700 DEG C, and calcination time is 5 hours, is cooled to room temperature, takes out sample; Be placed in atmosphere furnace after it again fully being ground, (be embedded in activated carbon powder) calcining under reducing atmosphere, calcining heat is 850 DEG C, and calcination time is 10 hours, namely obtains powder shaped chlorate luminescent material.Its main structural behaviour, excitation spectrum are similar to embodiment 4 with luminescent spectrum.
Claims (10)
1. a Chlorine borate luminescent material, is characterized in that: it is with Eu
2+for active ions, chemical general formula is M
3-3xeu
3xb
7o
13cl, wherein, M is Mg
2+, Zn
2+in one, 0.001≤x≤0.25.
2. the preparation method of a kind of Chlorine borate luminescent material as claimed in claim 1, it is characterized in that adopting high temperature solid-phase sintering synthesis, concrete steps are as follows:
(1) with the compound containing M ion, containing europium ion Eu
3+compound, containing boron ion B
3+compound, containing chloride ion Cl
-compound be raw material, by chemical general formula M
3-3xeu
3xb
7o
13cl takes each raw material, and wherein, 0.001≤x≤0.25, M is magnesium ion Mg
2+, zinc ion Zn
2+in one; Mix after the raw material taken is ground respectively;
(2) mixture step (1) obtained is first time calcining in air atmosphere, and calcining heat is 300 ~ 600 DEG C, and calcination time is 1 ~ 10 hour;
(3) mixture step (2) obtained second time calcining in air atmosphere, calcining heat is 600 ~ 800 DEG C, and calcination time is 1 ~ 10 hour;
(4), after naturally cooling, grind and mix, under reducing atmosphere third firing, calcining heat is 800 ~ 1000 DEG C, and calcination time is 1 ~ 10 hour, obtains a kind of Chlorine borate luminescent material.
3. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: the reducing atmosphere described in step (4) for be obtained by activated carbon powder, carbon black combustion method, or is nitrogen/hydrogen mixed gas.
4. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: M is magnesium ion Mg
2+compound be one in magnesium oxide, basic magnesium carbonate, magnesium chloride, magnesium hydroxide, magnesium nitrate or any two kinds.
5. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: M is zinc ion Zn
2+compound be one in zinc oxide, zinc carbonate, zinc chloride, zinc hydroxide, zinc nitrate or any two kinds.
6. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: containing europium ion Eu
3+compound be one in europium oxide, europium nitrate.
7. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: containing boron ion B
3+compound be one in boron oxide, boric acid.
8. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: the temperature that first time calcines is 350 ~ 600 DEG C, and calcination time is 3 ~ 8 hours.
9. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: the temperature of second time calcining is 620 ~ 750 DEG C, and calcination time is 3 ~ 8 hours.
10. the preparation method of a kind of Chlorine borate luminescent material according to claim 2, is characterized in that: the temperature of calcining under reducing atmosphere is 800 ~ 950 DEG C, and calcination time is 3 ~ 10 hours.
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| US3925537A (en) * | 1971-09-17 | 1975-12-09 | Du Pont | Metal boracites |
| CN101985553A (en) * | 2009-09-29 | 2011-03-16 | 鹤壁佳多科工贸有限责任公司 | Method for preparing europium excited calcium chloroborate blue fluorescent powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3925537A (en) * | 1971-09-17 | 1975-12-09 | Du Pont | Metal boracites |
| CN101985553A (en) * | 2009-09-29 | 2011-03-16 | 鹤壁佳多科工贸有限责任公司 | Method for preparing europium excited calcium chloroborate blue fluorescent powder |
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