CN100519693C - Alkaline earth phosphate long afterglow luminous material and its preparing method - Google Patents

Alkaline earth phosphate long afterglow luminous material and its preparing method Download PDF

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CN100519693C
CN100519693C CNB2005101190822A CN200510119082A CN100519693C CN 100519693 C CN100519693 C CN 100519693C CN B2005101190822 A CNB2005101190822 A CN B2005101190822A CN 200510119082 A CN200510119082 A CN 200510119082A CN 100519693 C CN100519693 C CN 100519693C
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reducing atmosphere
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alkaline earth
powder
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CN1775902A (en
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苏锵
刘丽艳
李成宇
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to an alkali soil phosphate long afterglow emitting material and the method to manufacture that belongs to emitting material field. it is made up from weighting according to the ratio and grinding to equal, sintering for 5-12h under 950-1200 degree centigrade or 3-6h under 300-600 degree centigrade, cooling to room temperature, grinding again and sintering for 5-12h in reducing atmosphere to gain compounding. The emitting light could be from magenta to blue, and the afterglow could last for 5 hours.

Description

A kind of alkaline earth phosphate long afterglow luminous material and preparation method
Technical field
The present invention relates to a kind of alkaline earth phosphate purple and blue long afterflow luminescent material and preparation method, belong to the luminescent material technical field.
Background technology
Long after glow luminous material claims noctilucent material again, and it is that a class absorbs the light that sunlight or source of artificial light produced, and sends visible light, and still can continue luminous material after stopping exciting.Having the daylight of utilization or light storage light, night or in the luminous characteristics in dark place is a kind of energy storage, energy-conservation luminescent material.Long-afterglow material application aspect low light level illumination, demonstration is very extensive, and its product such as luminous template, luminous paint, luminous printing ink, luminescent plastics, luminescent ceramic, luminous chemical fibre, luminous safety notice etc. are used for industry-by-industries such as communications and transportation, fire-fighting emergent safety, national defense and military, textiles and finishing material in a large number.
The development of long-afterglow material has very long history, people's research early be the sulfide long-afterglow material, as alkaline earth zinc sulphide etc.But there is significant disadvantages in this material, supports as after-glow brightness, and time of persistence is short, poor chemical stability, easy deliquescence etc.Can be by adding radioelement.Means such as material coated overcome these shortcomings; But the adding of radioelement all works the mischief to HUMAN HEALTH and environment, and the use of this material is subjected to very big restriction.
The mid-90, found new type long-persistence material SrAl 2O 4: Eu 2+, Dy 3+(2670-2673 pages of 1996 the 143rd volumes of J.Electrochem.Soc.), after UV-light or day optical excitation, the persistent green long afterglow of energy emitting bright, its after-glow brightness height, the time is long, and materials chemistry stability is all considerably beyond the sulfide long-afterglow material.
In recent years, be that the long-afterglow material of matrix also successively has been in the news with silicate.The silicate long-afterglow material is disclosed as patent CN98105870.6 and CN200380801922.6.This long-afterglow material has superior stability, but after-glow brightness and time are no more than aluminate long afterglow materials.
The report that with phosphoric acid salt is the long-afterglow material of matrix is seldom.Chinese patent CN03109879.7 has reported a kind of zinc phosphate long after glow luminous material and preparation method thereof.The selected substrate material of this invention is the zinc phosphate of different chemical structures.Different phase structures makes long-afterglow material present distinct colors, and yellow-green colour, orange-yellow and red three kinds of colors are arranged.
Summary of the invention
The invention provides a kind of alkaline earth phosphate long afterglow luminous material and preparation method.The invention provides a new steady persistence substrate material, and, can regulate the afterglow color by selecting different alkaline earth ions.
The selected substrate material of the present invention is a mixed alkaline earth cationic phosphoramidate hydrochlorate.Main active ions are europium ions.Auxiliary active ions are one or more the lower valency and the metal ion of high valence state.After the matrix absorption part energy, a part can shift and be caught by auxiliary activator, subsequently, under thermal excitation, gives the dominant activator ion in the slow release of room temperature and with transmission ofenergy.At last, by europium ion emission twilight sunset.By the kind of alkaline earth cation in the control matrix, this system can be launched purple light or blue light.
A kind of alkaline earth phosphate long afterglow luminous material of the present invention, it can be with following chemical formulation:
R (1-x-y±m)M 2±m(PO 4) 2:xEu，yN
In the formula: R is a kind of alkaline earth cation Ca, Sr or Ba, and M is alkaline earth cation Mg, and N is auxiliary active ions; N is one or more positively charged ions among Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Ti and the Zr when R is Sr or Ba, and N is one or more positively charged ions among Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Si, Ge, Sn, Sb, Bi, Ti and the Zr when R is Ca; X, y refer to the molar fraction of corresponding dopant ion, and x=0.001-0.2, y=0.02-0.2, m are Mg ionic molar fraction excessive or in shortage, m=0-0.1.
A kind of preparation method of alkaline earth phosphate long afterglow luminous material is as follows: the carbonate, oxide compound, the phosphatic raw materials that take by weighing respective element in aforesaid composition and ratio, after its grinding and mixing, directly in 950-1200 ℃ of sintering 5-12h or at 300-600 ℃ of pre-burning 3-6h, be cooled to room temperature, behind the regrinding, in reducing atmosphere,, make the purpose compound in 950-1200 ℃ of sintering 5-12h.
Preparation method of the present invention is simple, and the long-afterglow material that makes can present purple light or blue light distinct colors, and twilight sunset is bright, sustainable at least 5 hours of time of persistence.Can excite with daylight; Simultaneously, this long-afterglow material preparation technology's production cost is low, and product chemistry stable in properties is "dead", can not work the mischief to human and environment.Long after glow luminous material of the present invention application aspect low light level illumination, demonstration is very extensive, and its product such as luminous template, luminous paint, luminous printing ink, luminescent plastics, luminescent ceramic, luminous chemical fibre, luminous safety notice etc. can be used for industry-by-industries such as communications and transportation, fire-fighting emergent safety, national defense and military, textiles and finishing material in a large number.
Description of drawings
Fig. 1 is long persistence phosphor R 0.97Mg 2(PO 4) 2: Eu 0.01, the twilight sunset emission spectrum of Gd 0.02, a:R=Srb:R=Bac:R=Ca.
Fig. 2 is long persistence phosphor R 0.97Mg 2(PO 4) 2: Eu 0.01, the decay of afterglow curve of Gd 0.02, a:R=Srb:R=Bac:R=Ca.
Embodiment
By following examples to inventing further elaboration.
Embodiment 1
According to chemical formula Ca 0.97Mg 2(PO 4) 2: 0.01 Eu, 0.02 Gd accurately claims lime carbonate CaCO 30.00485mol (0.4850g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 300 ℃ of presintering 6 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 12 hours down at 950 ℃, sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 2
According to chemical formula Ca 0.975Mg 2(PO 4) 2: 0.005Eu, 0.02La accurately claims calcium oxide CaO0.004875mol (0.2764g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), ammonium di-hydrogen phosphate NH 4H 2PO 40.01mol (1.1503g), lanthanum trioxide La 2O 30.00005mol (0.0163g), europium sesquioxide Eu 2O 30.0000125mol (0.0044g), fully behind the mixing, under the nitrogen reducing atmosphere, 400 ℃ of presintering 4 hours, after being cooled to room temperature, take out sample, fully grind once more and in the nitrogen reducing atmosphere, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is CaMg 2(PO 4) 2
Embodiment 3
According to chemical formula Ca 0.96Mg 2(PO 4) 2: 0.02Eu, 0.02Al accurately claims lime carbonate CaCO 30.0048mol (0.4800g), magnesium oxide MgO 0.01mol (0.4030g), Vanadium Pentoxide in FLAKES P 2O 50.005mol (0.7097g), aluminium oxide Al 2O 30.00005mol (0.0051g), europium sesquioxide Eu 2O 30.00005mol (0.0176g), fully behind the mixing, under hydrogen reducing atmosphere, 600 ℃ of presintering 2 hours, after being cooled to room temperature, take out sample, fully grind once more and in hydrogen reducing atmosphere, reaction made in 8 hours under 1050 ℃, and sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 4
According to chemical formula Ca 0.97Mg 2(PO 4) 2: 0.01Eu, 0.02Ti accurately claim lime carbonate CaCO 30.00485mol (0.4850g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), titanium dioxide TiO 20.0001mol (0.0080g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 5 hours down at 1200 ℃, sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 5
According to chemical formula Ca 0.95Mg 2.2 (PO 4) 2: 0.01Eu, 0.02Ti accurately claim lime carbonate CaCO 30.00475mol (0.4750g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.0022mol (1.1081g), DAP (NH 4) 2HPO 40.01mol (1.3206g), titanium dioxide TiO 20.0001mol (0.0080g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 6
According to chemical formula Ca 0.94Mg 2(PO 4) 2: 0.04Eu, 0.02Dy accurately claims lime carbonate CaCO 30.0047mol (0.4700g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), dysprosium oxide Dy 2O 30.00005mol (0.0187g), europium sesquioxide Eu 2O 30.0001mol (0.0176g), fully behind the mixing, under the reducing atmosphere of hydrogen and nitrogen mixture, 500 ℃ of presintering 3 hours, be cooled to room temperature after, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is CaMg 2(PO 4) 2
Embodiment 7
According to chemical formula Ca 0.975Mg 2(PO 4) 2: 0.1 Eu, 0.005 Tb, 0.02 Li accurately claims lime carbonate CaCO 30.004875mol (0.4875g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), Quilonum Retard Li 2CO 30.00005mol (0.0037g), terbium sesquioxide Tb 4O 70.00000625mol (0.0047g), europium sesquioxide Eu 2O 30.00025mol (0.0815g), fully behind the mixing, under the air atmosphere, 600 ℃ of presintering 2 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is SrMg 2(PO 4) 2
Embodiment 8
According to chemical formula Ca 0.89Mg 2(PO 4) 2: 0.01 Eu, 0.10 Ho accurately claims lime carbonate CaCO 30.00445mol (0.4450g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), Holmium trioxide Ho 2O 30.00025mol (0.0945g), europium sesquioxide Eu 2O 30.000025mol (0.0081g), fully behind the mixing, under air atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is CaMg 2(PO 4) 2
Embodiment 9
According to chemical formula Ca 0.77Mg 2.2(PO 4) 2: 0.01 Eu, 0.02 Gd accurately claims lime carbonate CaCO 30.00385mol (0.3850g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.0022mol (1.1081g), DAP (NH 4) 2HPO 40.01mol (1.3206g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 10
According to chemical formula Ca 0.97Mg 2(P 0.95B 0.05O 4) 2: 0.01 Eu, 0.02 Gd accurately claims lime carbonate CaCO 30.00485mol (0.4850g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.0095mol (1.2546g), boron oxide B 2O 30.00025mol (0.0174g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 11
According to chemical formula Ca 0.97Mg 2(P 0.95B 0.05O 4) 2: 0.01 Eu, 0.02 Gd accurately claims lime carbonate CaCO 30.00485mol (0.4850g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.0095mol (1.2546g), boric acid H 3BO 30.0005mol (0.0309g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under air atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 7 hours down at 1100 ℃, sample mainly is CaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 12
According to chemical formula Sr 0.97Mg 2(PO 4) 2: 0.01Eu, 0.02Gd accurately claim Strontium carbonate powder SrCO 30.00485mol (0.7160g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 300 ℃ of presintering 6 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 12 hours down at 950 ℃, sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 13
According to chemical formula Sr 0.975Mg 2(PO 4) 2: 0.005 Eu, 0.02 La accurately claims strontium oxide SrO0.004875mol (0.5052g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), ammonium di-hydrogen phosphate NH 4H 2PO 40.01mol (1.1503g), lanthanum trioxide La 2O 30.00005mol (0.0163g), europium sesquioxide Eu 2O 30.0000125mol (0.0044g), fully behind the mixing, under the nitrogen reducing atmosphere, 400 ℃ of presintering 4 hours, after being cooled to room temperature, take out sample, fully grind once more and in the nitrogen reducing atmosphere, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is SrMg 2(PO 4) 2
Embodiment 14
According to chemical formula Sr 0.96Mg 2(PO 4) 2: 0.02 Eu, 0.02 Al accurately claims Strontium carbonate powder SrCO 30.0048mol (0.7086g), magnesium oxide MgO 0.01mol (0.4030g), Vanadium Pentoxide in FLAKES P 2O 50.005mol (0.7097g), aluminium oxide Al 2O 30.00005mol (0.0051g), europium sesquioxide Eu 2O 30.00005mol (0.0176g), fully behind the mixing, under hydrogen reducing atmosphere, 600 ℃ of presintering 2 hours, after being cooled to room temperature, take out sample, fully grind once more and in hydrogen reducing atmosphere, reaction made in 8 hours under 1050 ℃, and sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 15
According to chemical formula Sr 0.97Mg 2(PO 4) 2: 0.01 Eu, 0.02 Ti accurately claims Strontium carbonate powder SrCO 30.00485mol (0.7160g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), titanium dioxide TiO 20.0001mol (0.0080g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 7 hours down at 1100 ℃, sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 16
According to chemical formula Sr 0.95Mg 2.2(PO 4) 2: 0.01 Eu, 0.02 Ti accurately claims Strontium carbonate powder SrCO 30.00475mol (0.7012g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.0022mol (1.1081g), DAP (NH 4) 2HPO 40.01mol (1.3206g), titanium dioxide TiO 20.0001mol (0.0080g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under air atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 17
According to chemical formula Sr 0.94Mg 2(PO 4) 2: 0.04 Eu, 0.02 Dy accurately claims Strontium carbonate powder SrCO 30.0047mol (0.6939g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), dysprosium oxide Dy 2O 30.00005mol (0.0187g), europium sesquioxide Eu 2O 30.0001mol (0.0176g), fully behind the mixing, under the reducing atmosphere of hydrogen and nitrogen mixture, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is SrMg 2(PO 4) 2
Embodiment 18
According to chemical formula Sr 0.975Mg 2(PO 4) 2: 0.1 Eu, 0.005 Tb, 0.02 Li accurately claims Strontium carbonate powder SrCO 30.004875mol (0.7197g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), Quilonum Retard Li 2CO 30.00005mol (0.0037g), terbium sesquioxide Tb 4O 70.00000625mol (0.0047g), europium sesquioxide Eu 2O 30.00025mol (0.08145g), fully behind the mixing, under the charcoal reducing atmosphere, 600 ℃ of presintering 2 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is SrMg 2(PO 4) 2
Embodiment 19
According to chemical formula Sr 0.89Mg 2(PO 4) 2: 0.01 Eu, 0.10 Ho accurately claims Strontium carbonate powder SrCO 30.00445mol (0.6570g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), Holmium trioxide Ho 2O 30.00025mol (0.0945g), europium sesquioxide Eu 2O 30.000025mol (0.0081g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 5 hours down at 1200 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is SrMg 2(PO 4) 2
Embodiment 20
According to chemical formula Sr 0.77Mg 2.2(PO 4) 2: 0.01 Eu, 0.02 Gd accurately claims Strontium carbonate powder SrCO 30.00385mol (0.5684g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.0022mol (1.1081g), DAP (NH 4) 2HPO 40.01mol (1.3206g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 21
According to chemical formula Sr 0.97Mg 2(P 0.95B 0.05O 4) 2: 0.01 Eu, 0.02 Gd accurately claims Strontium carbonate powder SrCO 30.00485mol (0.7160g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.0095mol (1.2546g), boron oxide B 2O 30.00025mol (0.0174g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 22
According to chemical formula Sr 0.97Mg 2(P 0.95B 0.05O 4) 2: 0.01 Eu, 0.02 Gd accurately claims Strontium carbonate powder SrCO 30.00485mol (0.7160g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.0095mol (1.2546g), boric acid H 3BO 30.0005mol (0.0309g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under air atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is SrMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 23
According to chemical formula Ba 0.97Mg 2(PO 4) 2: 0.01 Eu, 0.02 Gd accurately claims barium carbonate BaCO 30.00485mol (0.9571g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 300 ℃ of presintering 6 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 12 hours down at 950 ℃, sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 24
According to chemical formula Ba 0.975Mg 2(PO 4) 2: 0.005 Eu, 0.02 Ce accurately claims barium oxide BaO0.004875mol (0.7475g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), ammonium di-hydrogen phosphate NH 4H 2PO 40.01mol (1.1503g), cerium oxide CeO 20.0001mol (0.0172g), europium sesquioxide Eu 2O 30.0000125mol (0.0044g), fully behind the mixing, under the nitrogen reducing atmosphere, 400 ℃ of presintering 4 hours, after being cooled to room temperature, take out sample, fully grind once more and in the nitrogen reducing atmosphere, reacted 8 hours down at 1050 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is BaMg 2(PO 4) 2
Embodiment 25
According to chemical formula Ba 0.96Mg 2(PO 4) 2: 0.02 Eu, 0.02 Ga accurately claims barium carbonate BaCO 30.0048mol (0.9472g), magnesium oxide MgO 0.01mol (0.4030g), Vanadium Pentoxide in FLAKES P 2O 50.005mol (0.7097g), gadolinium sesquioxide Ga 2O 30.00005mol (0.0094g), europium sesquioxide Eu 2O 30.00005mol (0.0176g), fully behind the mixing, under hydrogen reducing atmosphere, 600 ℃ of presintering 2 hours, after being cooled to room temperature, take out sample, fully grind once more and in hydrogen reducing atmosphere, reaction made in 7 hours under 1100 ℃, and sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 26
According to chemical formula Ba 0.97Mg 2(PO 4) 2: 0.01 Eu, 0.02 Ti accurately claims barium carbonate BaCO 30.00485mol (0.9571g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), titanium oxide TiO 20.0001mol (0.0080g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 5 hours down at 1200 ℃, sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 27
According to chemical formula Ba 0.95Mg 2.2(PO 4) 2: 0.01 Eu, 0.02 Ti accurately claims barium carbonate BaCO 30.00475mol (0.9374g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.0022mol (1.1081g), DAP (NH 4) 2HPO 40.01mol (1.3206g), titanium oxide TiO 20.0001mol (0.0080g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under air atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 28
According to chemical formula Ba 0.94Mg 2(PO 4) 2: 0.04 Eu, 0.02 Dy accurately claims barium carbonate BaCO 30.0047mol (0.9275g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), dysprosium oxide Dy 2O 30.00005mol (0.0187g), europium sesquioxide Eu 2O 30.0001mol (0.0176g), fully behind the mixing, under the reducing atmosphere of hydrogen and nitrogen mixture, reacted 7 hours down at 1100 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is BaMg 2(PO 4) 2
Embodiment 29
According to chemical formula Ba 0.975Mg 2(PO 4) 2: 0.1 Eu, 0.005 Tb, 0.02 Li accurately claims barium carbonate BaCO 30.004875mol (0.9620g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), Quilonum Retard Li 2CO 30.00005mol (0.0037g), terbium sesquioxide Tb 4O 70.00000625mol (0.0047g), europium sesquioxide Eu 2O 30.00025mol (0.08145g), fully behind the mixing, under the charcoal reducing atmosphere, 600 ℃ of presintering 2 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1050 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is BaMg 2(PO 4) 2
Embodiment 30
According to chemical formula Ba 0.89Mg 2(PO 4) 2: 0.01 Eu, 0.10 Ho accurately claims barium carbonate BaCO 30.00445mol (0.8782g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.01mol (1.3206g), europium sesquioxide Ho 2O 30.00025mol (0.0945g), europium sesquioxide Eu 2O 30.000025mol (0.0081g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 6 hours down at 1150 ℃, sample is through powder x x ray diffraction analysis x, and principal phase is BaMg 2(PO 4) 2
Embodiment 31
According to chemical formula Ba 0.77Mg 2.2(PO 4) 2: 0.01 Eu, 0.02 Gd accurately claims barium carbonate BaCO 30.00385mol (0.7598g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.0022mol (1.1081g), DAP (NH 4) 2HPO 40.01mol (1.3206g), gadolinium sesquioxide Gd 2O 30.00005mol (0.01813g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 32
According to chemical formula Ba 0.97Mg 2(P 0.95B 0.05O 4) 2: 0.01 Eu, 0.02 Gd accurately claims barium carbonate BaCO 30.00485mol (0.9571g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.0095mol (1.2546g), boron oxide B 2O 30.00025mol (0.0174g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, 1000 ℃ were reacted 10 hours down, and sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2
Embodiment 33
According to chemical formula Ba 0.97Mg 2(P 0.95B 0.05O 4) 2: 0.01Eu, 0.02Gd accurately claims barium carbonate BaCO 30.00485mol (0.9571g), magnesium basic carbonate Mg (OH) 24MgCO 36H 2O0.002mol (1.0073g), DAP (NH 4) 2HPO 40.0095mol (1.2546g), boric acid H 3BO 30.0005mol (0.0309g), gadolinium sesquioxide Gd 2O 30.00005mol (0.0181g), europium sesquioxide Eu 2O 30.000025mol (0.0088g), fully behind the mixing, under the charcoal reducing atmosphere, 500 ℃ of presintering 3 hours, after being cooled to room temperature, take out sample, fully grind once more and in the charcoal reducing atmosphere, reacted 10 hours down at 1000 ℃, sample mainly is BaMg through powder x x ray diffraction analysis x mutually 2(PO 4) 2

Claims (4)

1, a kind of alkaline earth phosphate long afterglow luminous material is characterized in that, it is with following chemical formulation:
R (1-x-y±m)M 2±m(PO 4) 2:xEu，yN
In the formula: R is a kind of alkaline earth cation Ca, Sr or Ba, and M is alkaline earth cation Mg, and N is auxiliary active ions; N is one or more positively charged ions among Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Ti and the Zr when R is Sr or Ba, and N is one or more positively charged ions among Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Si, Ge, Sn, Sb, Bi, Ti and the Zr when R is Ca; X, y refer to the molar fraction of corresponding dopant ion, and x=0.001-0.2, y=0.02-0.2, m are Mg ionic molar fraction excessive or in shortage, m=0-0.1.
2, a kind of alkaline earth phosphate long afterglow luminous material as claimed in claim 1 is characterized in that, it is with following chemical formulation: Sr 0.97Mg 2(PO 4) 2: Eu0.01, Gd0.02.
3, a kind of alkaline earth phosphate long afterglow luminous material as claimed in claim 1 is characterized in that, it is with following chemical formulation: Ba 0.97Mg 2(PO 4) 2: Eu0.01, Gd0.02.
4, a kind of alkaline earth phosphate long afterglow luminous material as claimed in claim 1 is characterized in that, it is with following chemical formulation: Ca 0.97Mg 2(PO 4) 2: Eu0.01, Gd0.02.
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