CN101104547B - White light radiation glass for rare earth ion europium activating lamp and preparation method thereof - Google Patents

White light radiation glass for rare earth ion europium activating lamp and preparation method thereof Download PDF

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Publication number
CN101104547B
CN101104547B CN2007100621859A CN200710062185A CN101104547B CN 101104547 B CN101104547 B CN 101104547B CN 2007100621859 A CN2007100621859 A CN 2007100621859A CN 200710062185 A CN200710062185 A CN 200710062185A CN 101104547 B CN101104547 B CN 101104547B
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glass
rare earth
white light
preparation
earth metal
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CN101104547A (en
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廉志红
沈毅
孙小星
刘会欣
黎月英
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Hebei University of Science and Technology
Hebei Polytechnic University
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Hebei University of Science and Technology
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Abstract

The present invention discloses a rare earth ions europium activated lamp-use glass which emits white light, as well as the related preparation method. The chemical composition of the glass is aMO-bB2O3-cP2O5:dEuO, wherein, the aMO-bB2O3-cP2O5 is glass matrix; Eu2+ is luminescence ion; M is one of or more of alkaline earth metal ions Ca, Ba and Sr; a, b, c, d are the correspondingly composed molepercentage coefficient. The preparation method is that alkaline earth metal carbonate, boron oxide, alkaline-earth metal hydrogen phosphate salt and europium oxide are measured according to the composition and proportion of the glass and are fully grinded and uniformly mixed; the mixture will then be fused at 1100 to 1500 DEG C under the reducing condition or in the air for 1 to 5 hours; the glass melting liquid is molded and annealed to get the final product. The invention can directly prepare Eu2+ under weak oxidation atmosphere conditions in the air by changing the glass matrix composition, and make the single rare earth ion Eu2 + directly mix into the glass to get the glass that emits white light. The invention has the advantages of high concentration of the rare earth ions and high brightness, which omits the past bepowdering technology, simplifies the technology process and reduces the production costs.

Description

White light radiation glass for rare earth ion europium activating lamp and preparation method thereof
Technical field:
The present invention relates to the to emit white light preparation method of glass, especially a kind of white light radiation glass for rare earth ion europium activating lamp and preparation method thereof.
Background technology:
At lighting field, the topmost application facet of rare earth luminescent material is power saving fluorescent lamp, cold-cathode fluorescence lamp, high voltage mercury lamp, metal halide lamp, semiconductor light source, planar light source etc.1973, Dutch Philips company at first proposed the phosphor of rare earth.The phosphor of rare earth is made up of three kinds of fluorescent material of rare-earth ion activated red, green, blue.The basic structure of three-color fluorescent lamp, preparation technology and principle of luminosity are: coat the red, green, blue three primary colors fluorescent powder at tube inner wall, after the energising, mercury or rare gas element in the fluorescent tube are subjected to electron excitation to give off UV-light, fluorescent material on the ultraviolet excitation fluorescent tube, launch red, green, blue respectively, the proportioning that the choose reasonable allotment is three primary colors luminous, thus white light obtained.It is main that the light emitting ionic of three primary colors fluorescent powder is generally rare earth ion.The rare-earth trichromatic fluorescent powder of present commercial applications: rouge and powder is Y 2O 3: Eu, green powder are CeMgAl 11O 19: Tb or (La, Ce, Tb) PO 4, blue powder is BaMgAl 10O 17: Eu.Because its light efficiency and photochromic while can reach higher level, and are regarded as the advanced luminescent material of green energy conservation, therefore development is very fast, has become current extremely important lamp phosphor.But rare-earth trichromatic fluorescent powder is made up of three kinds of fluorescent material of red, green, blue, the synthesis technique difference of each luminescent powder, and the selection of building-up process temperature, time, atmosphere all can be played tangible influence to the quality of fluorescent material.
The common valence state of rare earth ion is+3 valencys, obtains the method for improper valence state rare earth ion, mainly sets up according to the normal valence state ion condition that the gain and loss electron institute needs in compound, promptly selects suitable oxidation or reduction approach.Obtain for the bivalent rare earth ionic, the normal method of reducing that adopts has: feed H in the high-temperature reaction process 2, H 2/ N 2, NH 3Or gas such as CO; High temperature sintering under activated carbon exists; Directly mix reductive agent etc. in the reactant.Journal of Luminescence report Tale in 1979 does not adopt any method of reducing under extraneous air atmosphere, synthesized Eu by high temperature solid state reaction 2+Adulterated Ba 3(PO4) 2, for bivalent rare earth ionic preparation provides a safety, novel method easily.Changchun should change systematically studied under the air conditions rare earth ion Eu for many years in the redox of systems such as borate, phosphoric acid salt, borophosphate, aluminate, silicate.Though this method has caused the interest of a lot of researchers, the luminous of+divalent europium mostly is blue, green.
Summary of the invention:
The purpose of this invention is to provide a kind of white light radiation glass for rare earth ion europium activating lamp and preparation method thereof.It is by changing the composition of glass matrix, realizes directly firing under the weak oxide atmospheric condition of air ambient+europium of divalent, and with this single rare earth ion Eu 2+Directly mix the glass that glass must be sent out equal white light.Solved and luminescent powder has been coated onto the loaded down with trivial details technology of making the glass that emits white light on the fluorescent tube in the past, and+the luminous of divalent europium is the d-d transition, luminous efficiency height, glass middle-weight rare earths ionic doping content height, then the luminosity height of glass.
The technical solution used in the present invention is:
A kind of white light radiation glass for rare earth ion europium activating lamp, the chemical constitution of this glass is: aMO-bB 2O 3-cP 2O 5: dEuO; AMO-bB wherein 2O 3-cP 2O 5Be glass matrix, Eu 2+Be light emitting ionic, M is one or more among alkaline-earth metal ions Ca, Ba, the Sr; A, b, c, d are the molar percentage coefficient of corresponding composition, 0.340≤a≤0.550; 0.250≤b≤0.450; 0.200≤c≤0.360; 0.001≤d≤0.200.
The preparation method of this glass is: take by weighing alkaline earth metal carbonate, boron oxide, alkaline-earth metal hydrophosphate, europium sesquioxide in glass composition and ratio, fully ground and mixed is even, then under reductive condition or under air conditions 1100-1500 ℃ fusion 1-5 hour, again with the moulding of glass melting liquid, through annealing, obtain the finished product.
In the such scheme, the not only available method of reducing of the europium of+divalent makes, and can also directly fire acquisition under the weak oxide atmospheric condition of air ambient.
Compare with background technology, the present invention is owing to be that the single rare earth ion emits white light, overcome existing luminescent lamp three primary colors fluorescent powder in use because the synthesis technique difference of each luminescent powder, the variation of the quality of the selection of building-up process temperature, time, atmosphere and the fluorescent material that causes; Simultaneously because direct preparation fluorescent glass, doping concentration of rare earth ion height not only, the luminosity height, and remove coating process from, the simplification technological process reduces production costs.
Description of drawings:
Fig. 1 is the luminescent spectrum figure of glass of the present invention under ultraviolet excitation.
Embodiment:
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1:
Come each component of this glass composition of weighing by following molar content:
CaO：0.350； B 2O 3：0.400；
NH 4H 2P 2O 5：0.250； Eu 2O 3：0.001。
Will be by the accurate weighing CaCO of ratio of components 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, in stove, feed hydrogen behind the levigate mixing as reducing atmosphere, in 1500 ℃ of constant temperature 5.0h.Glass is come out of the stove after moulding, annealing obtain the finished product.
Embodiment 2:
Come each component of this glass composition of weighing by following molar content:
SrO：0.450； B 2O 3：0.250；
NH 4H 2P 2O 5：0.300； Eu 2O 3：0.010。
Will be by the accurate weighing BaCO of ratio of components 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, in stove, feed CO gas behind the levigate mixing as reducing atmosphere, in 1300 ℃ of constant temperature 3.0h.Glass is come out of the stove after moulding, annealing obtain the finished product.
Embodiment 3:
Come each component of this glass composition of weighing by following molar content:
BaO：0.550； B 2O 3：0.280；
NH 4H 2P 2O 5：0.270； Eu 2O 3：0.010。
Will be by the accurate weighing BaCO of ratio of components 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, behind the levigate mixing, under air conditions, in 1100 ℃ of constant temperature 1.0h.Glass is come out of the stove after moulding, annealing obtain the finished product.
Embodiment 4:
Come each component of this glass composition of weighing by following molar content:
CaO：0.150； SrO：0.200；
B 2O 3：0.450； NH 4H 2P 2O 5：0.200；
Eu 2O 3：0.01。
Will be by the accurate weighing BaCO of ratio of components 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, behind the levigate mixing, under air conditions, in 1450 ℃ of constant temperature 4.0h.Glass is come out of the stove after moulding, annealing obtain the finished product.
Embodiment 5:
Come each component of this glass composition of weighing by following molar content:
CaO：0.160； SrO：0.180；
B 2O 3：0.300； NH 4H 2P 2O 5：0.360；
Eu 2O 3：0.005。
Will be by the accurate weighing CaCO of ratio of components 3, SrCO 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, behind the levigate mixing, under air conditions, in 1350 ℃ of constant temperature 2.0h.Glass is come out of the stove after moulding, annealing obtain the finished product.
Embodiment 6:
Come each component of this glass composition of weighing by following molar content:
SrO：0.200； BaO：0.200；
B 2O 3：0.330； NH 4H 2P 2O 5：0.270；
Eu 2O 3：0.050。
Will be by the accurate weighing SrCO of ratio of components 3, BaCO 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, behind the levigate mixing, under air conditions, in 1250 ℃ of constant temperature 1.5h.Glass is come out of the stove after moulding, annealing obtain the finished product.
Embodiment 7:
Come each component of this glass composition of weighing by following molar content:
CaO：0.150； SrO：0.150；
SrO：0.150； B 2O 3：0.260；
NH 4H 2P 2O 5：0.290； Eu 2O 3：0.010。
Will be by the accurate weighing CaCO of ratio of components 3, SrCO 3, BaCO 3, B 2O 3, NH 4H 2P 2O 5, Eu 2O 3, behind the levigate mixing, under air conditions, in 1300 ℃ of constant temperature 1.0h.Glass is come out of the stove after moulding, annealing obtain the finished product.

Claims (2)

1. white light radiation glass for rare earth ion europium activating lamp, it is characterized in that: the chemical constitution of this glass is: aMO-bB 2O 3-cP 2O 5: dEuO; AMO-bB wherein 2O 3-cP 2O 5Be glass matrix, Eu 2+Be light emitting ionic, M is one or more among alkaline-earth metal ions Ca, Ba, the Sr; A, b, c, d are the molar percentage coefficient of corresponding composition, 0.340≤a≤0.550; 0.250≤b≤0.450; 0.200≤c≤0.360; 0.001≤d≤0.200.
2. preparation method of white light radiation glass for rare earth ion europium activating lamp according to claim 1, it is characterized in that: take by weighing alkaline earth metal carbonate, boron oxide, alkaline-earth metal hydrophosphate, europium sesquioxide in glass composition and ratio, fully ground and mixed is even, then under reductive condition or under air conditions 1100-1500 ℃ fusion 1-5 hour, again with the moulding of glass melting liquid, through annealing, obtain the finished product.
CN2007100621859A 2007-06-16 2007-06-16 White light radiation glass for rare earth ion europium activating lamp and preparation method thereof Expired - Fee Related CN101104547B (en)

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CN102381841B (en) * 2010-08-31 2013-10-02 海洋王照明科技股份有限公司 Yellow green luminescent glass ceramic material and preparation method thereof
CN102408195B (en) * 2010-09-26 2013-10-02 海洋王照明科技股份有限公司 Borate luminescent glass and preparation method thereof
CN102173583B (en) * 2010-11-29 2013-02-20 天津理工大学 Rare earth activated white light luminescent glass material as well as preparation method and application thereof
CN102992618A (en) * 2012-12-25 2013-03-27 河北联合大学 Rare earth europium-doped nitrogen oxide luminescent glass and preparation method thereof
CN103130414B (en) * 2013-03-05 2014-12-24 中山大学 Rare earth-doped silicate luminescent glass and preparation method thereof
CN106630602B (en) * 2016-12-19 2019-09-13 温州大学 Photochromic adjustable agricultural fluorescent glass of one kind and preparation method thereof
CN106698934B (en) * 2016-12-19 2019-09-13 温州大学 A kind of Chlorine borate blue light glass and preparation method thereof for ultraviolet LED
CN107814484B (en) * 2017-11-16 2020-03-31 湖南师范大学 Europium ion self-reduction-capability-containing luminescent transparent glass and preparation method thereof

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Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US5322820A (en) * 1992-12-08 1994-06-21 Kigre, Inc. Athermal laser glass compositions with high thermal loading capacity
US5322820C1 (en) * 1992-12-08 2001-04-24 Kigre Inc Athermal laser glass compositions with high thermal loading capacity

Non-Patent Citations (2)

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Title
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