CN102408195B - Borate luminescent glass and preparation method thereof - Google Patents

Borate luminescent glass and preparation method thereof Download PDF

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CN102408195B
CN102408195B CN 201010292480 CN201010292480A CN102408195B CN 102408195 B CN102408195 B CN 102408195B CN 201010292480 CN201010292480 CN 201010292480 CN 201010292480 A CN201010292480 A CN 201010292480A CN 102408195 B CN102408195 B CN 102408195B
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preparation
glass
borate
fluorescent glass
borate fluorescent
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CN102408195A (en
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周明杰
乔延波
马文波
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to the field of luminescent materials, and discloses borate luminescent glass and a preparation method thereof. The borate luminescent glass has a general chemical formula of (50-x)In[2]O[3]-50B[2]O[3]-xRE[2]O[3], wherein 0<x<=10, RE is at least one of Eu ion or Tb ion, and preferably 2<x<=8. According to the invention, rare earth ion doped borate luminescent glass is prepared from InBO3:Eu and InBO3:Tb used as basis by a glass preparation process to obtain the luminescent glass with the component of (50-x)In[2]O[3]-50B[2]O[3]-xRE[2]O[3]. The rare earth ion doped borate luminescent glass can generate stronger visible light under the excitation of cathode ray, and can also generate stronger visible light under the excitation of ultraviolet light, purple light and bluelight.

Description

A kind of borate fluorescent glass and preparation method thereof
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of borate fluorescent glass.The invention still further relates to a kind of preparation method of borate fluorescent glass.
Background technology
The development of lighting engineering has brought developing rapidly of various system luminescent materials, and wherein the research and development of the luminescent material of borate salt system and application have great importance.The characteristics of borate salt system luminescent material be synthetic easy, calcining temperature is low, and can obtain the luminescent material of high brightness.Because the structure diversity of borate ion, to the research of rear-earth-doped borate material structure and spectral quality carry out a lot, also obtained some important achievement, as (Ce, Gd, Tb) MgB 5O 10Be a kind of efficient rare-earth three primary colors fluorescent powder of practicality, (Y, Gd) BO 3: Eu is the more rouge and powder that is used to color plasma display (PDP) also.InBO 3: Eu and InBO 3: Tb also is two kinds of fluorescent material that can be used to the luminous and photoluminescence of cathode-ray exciting, InBO 3: Eu among the Eu 3+Ply in the centre symmetrical case of ion produces extremely strong 5D 0→ 7F 1Transition luminescence, and at InBO 3: Tb among the Tb 3+What ion presented is extremely strong 5D 0→ 7F 5Emission.Yet along with the continuous development of light source kind and encapsulation technology, increasing fluorescent material can not satisfy research and requirement of actual application, and the improving constantly to press for of demand carried out block materials, even the research of transparent luminescent material.Patent of the present invention is exactly based on borate fluorescent powder, by the development glasswork, proposes a kind of borate fluorescent glass and preparation method thereof.
Summary of the invention
In order to address the above problem, the invention provides a kind of borate fluorescent glass, its chemical general formula is: (50-x) In 2O 3-50B 2O 3-xRE 2O 3Wherein, the value of x is 0＜x≤10, and RE is at least a in Eu ion or the Tb ion, and the value of preferred x is 2＜x≤8.
Another object of the present invention is to provide a kind of preparation method of borate fluorescent glass, preparation flow is as follows:
Step S1, according to chemical general formula (50-x) In 2O 3-50B 2O 3-xRE 2O 3In each component mole number, take by weighing the source compound of In (phosphide element, down with), the source compound of B (boron, down with) and the source compound of RE mix, grind to form mixed powder; Wherein, the value of x is 0＜x≤10, and RE is at least a in Eu (europium element, down with) ion or Tb (terbium element, the down with) ion;
Step S2, described mixed powder placed to take out after 1450-1600 ℃ of high-temperature fusion 1-5 hour be poured on that chilling forms glass on the steel plate;
Step S3, glass 500-900 ℃ of above-mentioned acquisition heat-treated 1-20 hour, after the cooling, make described borate fluorescent glass.
Among the above-mentioned steps S1, the source compound of In, the source compound of B and the source compound of RE are respectively In 2O 3, H 3BO 3, RE oxide compound.
Compared with prior art, the present invention has the following advantages:
The present invention is to provide a kind of rare earth ion doped borate fluorescent glass, with InBO 3: Eu and InBO 3: Tb fluorescent material is the basis, and obtaining component by glass preparation technology is (50-x) In 2O 3-50B 2O 3-xRE 2O 3Fluorescent glass.This rare earth ion doped borate glass can produce stronger as seen luminous under cathode-ray exciting; This rare earth ion doped borate glass is at UV-light, purple light and the stronger visible light of blue-light excited generation down.
Description of drawings
Fig. 1 is preparation technology's schema of borate fluorescent glass of the present invention;
The photoluminescence spectra of the fluorescent glass that Fig. 2 obtains for embodiment 1.
The cathodluminescence spectrum of the fluorescent glass that Fig. 3 obtains for embodiment 1.
The photoluminescence spectra of the fluorescent glass that Fig. 4 obtains for embodiment 2.
The cathodluminescence spectrum of the fluorescent glass that Fig. 5 obtains for embodiment 2.
Photoexcitation of the present invention and emmission spectrum are to adopt Tianjin, island RF-5301 fluorescence spectrophotometer to measure under normal temperature condition.
During the present invention increases in the cathodoluminescence spectrum test acceleration voltage of electron-beam excitation be 1.5Kv.
Embodiment
The invention provides a kind of borate fluorescent glass, its chemical general formula is: (50-x) In 2O 3-50B 2O 3-xRE 2O 3Wherein, the value of x is 0＜x≤10, and RE is at least a in Eu ion or the Tb ion, and the value of preferred x is 2＜x≤8.
The preparation method of above-mentioned a kind of borate fluorescent glass, as shown in Figure 1, preparation flow is as follows:
Step S1, according to chemical general formula (50-x) In 2O 3-50B 2O 3-xRE 2O 3In each component mole number, take by weighing the source compound of In, the source compound of B and the source compound of RE mix, grind to form mixed powder; Wherein, the value of x is 0＜x≤10, and RE is at least a in Eu ion or the Tb ion;
Step S2, described mixed powder placed to take out after 1450-1600 ℃ of high-temperature fusion 1-5 hour be poured on that chilling forms glass on the steel plate;
Step S3, glass 500-900 ℃ of above-mentioned acquisition heat-treated 1-20 hour, after the cooling, make described borate fluorescent glass.
Among the above-mentioned steps S1, preferred, the source compound of In, the source compound of B and the source compound of RE are respectively In 2O 3, H 3BO 3, RE oxide compound.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
With the chemical pure In of analytical balance difference weighing 2O 314.08g, H 3BO 36.96g and Eu 2O 31.98g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1550 ℃ of following fusions insulation 3h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 45In 2O 3-50B 2O 3-5Eu 2O 3Borate glass.With the glass furnace cooling behind insulation 5h under 500 ℃ that obtains, obtain the borate fluorescent glass of Eu ion doping, this fluorescent glass is in negative ray and the stronger red emission of blue-light excited generation down.
The photoluminescence spectra of the fluorescent glass that Fig. 2 obtains for embodiment 1, Ex1 is excitation spectrum among the figure, and the excitation peak wavelength location is positioned at 465nm, and Em1 is emmission spectrum, and the emission peak wavelength location is positioned at 612nm.
The cathodluminescence spectrum of the fluorescent glass that Fig. 3 obtains for embodiment 1, the glow peak wavelength is 612nm.
Embodiment 2
With the chemical pure In of analytical balance difference weighing 2O 314.03g, H 3BO 36.94g and Tb 4O 72.09g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1550 ℃ of following fusions insulation 5h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 45In 2O 3-50B 2O 3-5Tb 2O 3Borate glass.With the glass furnace cooling behind insulation 5h under 700 ℃ that obtains, obtain the borate fluorescent glass of Tb ion doping, this fluorescent glass is in negative ray and the stronger green emission of blue-light excited generation down.
The photoluminescence spectra of the fluorescent glass that Fig. 4 obtains for embodiment 2, Ex2 is excitation spectrum among the figure, and the excitation peak wavelength location is positioned at 485nm, and Em2 is emmission spectrum, and the emission peak wavelength location is positioned at 544nm.
The cathodluminescence spectrum of the fluorescent glass that Fig. 5 obtains for embodiment 2, the glow peak wavelength is 544nm.
Embodiment 3
With the chemical pure In of analytical balance difference weighing 2O 315.60g, H 3BO 37.09g and Eu 2O 30.40g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1470 ℃ of following fusions insulation 3h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 49In 2O 3-50B 2O 3-1Eu 2O 3Borate glass.With the glass furnace cooling behind insulation 6h under 650 ℃ that obtains, obtain the borate fluorescent glass of Eu ion doping.
Embodiment 4
With the chemical pure In of analytical balance difference weighing 2O 314.06g, H 3BO 36.95g, Eu 2O 30.99g and Tb 4O 71.05g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1450 ℃ of following fusions insulation 20h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 45In 2O 3-50B 2O 3-2.5Eu 2O 3-2.5Tb 2O 3Borate glass.Glass furnace cooling behind insulation 1h under 900 ℃ with obtaining obtains the ion co-doped borate fluorescent glass of Eu, Tb.
Embodiment 5
With the chemical pure In of analytical balance difference weighing 2O 315.19g, H 3BO 37.04g and Tb 4O 70.85g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1600 ℃ of following fusions insulation 1h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 48In 2O 3-50B 2O 3-2Tb 2O 3Borate glass.With the glass furnace cooling behind insulation 6h under 800 ℃ that obtains, obtain the borate green fluorescent glass of Tb ion doping.
Embodiment 6
With the chemical pure In of analytical balance difference weighing 2O 312.26g, H 3BO 36.82g and Eu 2O 33.88g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1500 ℃ of following fusions insulation 4h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 40In 2O 3-50B 2O 3-10Eu 2O 3Borate glass.With the glass furnace cooling behind insulation 5h under 600 ℃ that obtains, obtain the borate red fluorescent glass of Eu ion doping.
Embodiment 7
With the chemical pure In of analytical balance difference weighing 2O 312.94g, H 3BO 36.86g, Eu 2O 31.56g and Tb 4O 71.65g, place mortar fully to mix raw material, mixed raw material is poured in the corundum crucible.Raw material takes out behind 1520 ℃ of following fusions insulation 3h in High Temperature Furnaces Heating Apparatus and pours into steel plate and carry out chilling to obtain component be 42In 2O 3-50B 2O 3-4Eu 2O 3-4Tb 2O 3Borate glass.Glass furnace cooling behind insulation 20h under 500 ℃ with obtaining obtains the ion co-doped borate fluorescent glass of Eu, Tb.
Should be understood that above-mentioned statement at preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. borate fluorescent glass, its chemical general formula is: (50-x) In 2O 3-50B 2O 3-xRE 2O 3Wherein, the value of x is 0＜x≤10, and RE is at least a in Eu ion or the Tb ion; Described In 2O 3, B 2O 3With RE 2O 3Mol ratio be 50-x:50:x.
2. borate fluorescent glass according to claim 1 is characterized in that, the value of described x is 2＜x≤8.
3. the preparation method of a borate fluorescent glass is characterized in that, comprises the steps:
According to chemical general formula (50-x) In 2O 3-50B 2O 3-xRE 2O 3In each component mole number, take by weighing the source compound of In, the source compound of B and the source compound of RE mix, grind to form mixed powder; Wherein, the value of x is 0＜x≤10, and RE is at least a in Eu ion or the Tb ion;
Described mixed powder placed carry out melting treatment, fused solution is taken out form glass subsequently;
The glass of above-mentioned acquisition is heat-treated, after the cooling, make described borate fluorescent glass.
4. the preparation method of borate fluorescent glass according to claim 3 is characterized in that, the value of described x is 2＜x≤8.
5. the preparation method of borate fluorescent glass according to claim 3 is characterized in that, the source compound of described In is In 2O 3
6. the preparation method of borate fluorescent glass according to claim 3 is characterized in that, the source compound of described B is H 3BO 3
7. the preparation method of borate fluorescent glass according to claim 3 is characterized in that, the source compound of described RE is the oxide compound of RE.
8. the preparation method of borate fluorescent glass according to claim 3 is characterized in that, in the described melting treatment step, melt temperature is 1450～1600 ℃, and the fusion time is 1～20h.
9. according to the preparation method of claim 3 or 8 described borate fluorescent glasses, it is characterized in that the mode that described fused solution forms glass is with cooling mode fused solution to be formed glass at ice-cold steel plate.
10. the preparation method of borate fluorescent glass according to claim 3 is characterized in that, in the described heat treatment step, thermal treatment temp is 500～900 ℃, and heat treatment time is 1～20h.
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CN101104547A (en) * 2007-06-16 2008-01-16 河北理工大学 White light radiation glass for rare earth ion europium activating lamp and preparation method thereof

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