CN107722978A - A kind of multi-component oxide long after glow luminous material and preparation method thereof - Google Patents
A kind of multi-component oxide long after glow luminous material and preparation method thereof Download PDFInfo
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- CN107722978A CN107722978A CN201711029894.7A CN201711029894A CN107722978A CN 107722978 A CN107722978 A CN 107722978A CN 201711029894 A CN201711029894 A CN 201711029894A CN 107722978 A CN107722978 A CN 107722978A
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Abstract
The invention discloses a kind of multi-component oxide long after glow luminous material, the chemical expression of the luminescent material is（2‑a‑b）ZnO·（1‑c）SiO2·0.4cP2O5·aMgO·dB2O3, wherein a=0.005 ~ 0.1, b=0.002 ~ 0.09, c=0.01 ~ 0.15, d=0.05 ~ 0.2.The present invention, wherein using silicon, zinc oxide as material of main part, is suitably introduced into magnesium and boron oxide compound, first prepares product using continuation high-temperature calcination preparation technology under vacuum after high-temperature calcination under air atmosphere using multi-component oxide as host material.Prepared long after glow luminous material can continue green light more than 14 hours in the dark, for material using internal flaw as the centre of luminescence, luminescent properties are excellent, and chemically stable is good and cost is low after light-illuminating 15 minutes.
Description
Long after glow luminous material is that light-storing material is a kind of functional ceramic material, is a kind of absorption solar energy or artificial energy
Source, and excite stop after may continue to send the material of visible ray.Long after glow luminous material is widely used in emergency lighting and referred to
Show the fields such as equipment, display device, luminescent ceramic, luminous paint and optoelectronic information.In addition, long after glow luminous material is in solar-electricity
Also it is applied on pond, can also be applied to medical bio mark to realize the visualization of cancer cell diffusion.Long-afterglow material is main
It is made up of host material, activator (centre of luminescence) and auxiliary activator.Host material is the main composition portion of luminescent material
Point, there is important influence to the luminous and afterglow property of material.Rare earth ion and transition metal ions are conventional activator.It is auxiliary
Co-activator is generally acknowledged that it is not luminous or luminous very weak in itself in matrix, but it can effectively absorb excitation energy simultaneously
The centre of luminescence is passed it on, so that the afterglow property enhancing of material.Such as SrA12O4：Eu2+, Dy3+In, SrA12O4For matrix
Material, Eu2+For the centre of luminescence, Dy3+For auxiliary activator；Zn3(PO4)2：Mn2+, Pr3+In, Zn3(PO4)2For host material,
Mn2+For the centre of luminescence, sensitizer Pr3+To aid in Validation Counter.A kind of patent of invention " orange-yellow long-afterglow material（Application number：
201410791393.2）" disclose Li2Sr1-x-ySiO4：xEu2+, yR3+The preparation of orange-yellow long-afterglow material, wherein
Li2Sr1-x-ySiO4For host material, Eu2+For the centre of luminescence, R3+As auxiliary activator；Patent of invention " long-decay phosphor material
（Application number：98124888.8）" one kind is disclosed with europium (Eu2+), dysprosium (Dy3+) and cerium (Ce3+) alkaline earth as additional activation agent
The preparation of phosphorus aluminic acid long-decay phosphor material；Patent of invention a kind of " method of quickly synthesizing long-persistence luminescent material（Application number：
201010243006.3）" disclose a kind of quickly synthesizing long-persistence luminescent material Ca(0.8-2x) Zn0.2TiO3:xPr3+, xNa+'s
Preparation method, wherein Pr3+For the centre of luminescence, Na+Introducing is advantageous to improve fault in material concentration so as to improve the photism of material
Energy；A kind of patent of invention " red long afterglow luminous material and preparation method thereof（Application number：200910112064.X）" disclose
A kind of Mn2+Ion-activated red long afterglow luminous material (Zn1-α-βMnαLnβ)3（P1-0.8γSiγO4）2Preparation method, wherein Mn2 +Ion is the centre of luminescence, Ln is auxiliary activator；A kind of red long afterglow luminous material of patent of invention and preparation method thereof（Shen
Please number：201310089863.6）One kind is disclosed with Cr3+For the red long afterglow luminous material ZnGa of the centre of luminescence2O4：aCr3 +,bDy3+Preparation.These luminescent materials are using rare earth ion or some transition metal ions as the centre of luminescence.The present invention is with more
Component oxide is as host material, wherein using silicon, zinc oxide as material of main part, being suitably introduced into magnesium and boron oxide compound can be with
Structural behaviour and the crystal property of material are effectively improved so as to be advantageous to the improvement of material emission performance, the incorporation of P elements also can
It is effectively improved the luminescent properties of material.This material calcines 1-5 hours first in the air containing oxygen makes material be formed well
Structure and crystal property, then continue in a vacuum calcine 2-6 hours with manufacture material inside oxygen defect.Manufactured in material
Internal flaw and using defect capture photon with storage light, and having electronic and can occur in the material the defects of with hole migration and
Met in transition process and occur to destroy and light, i.e., the centre of luminescence is entirely defect without rare earth ion or transition metal
Ion, prepared material have the advantages such as luminescent properties are excellent, the cost of raw material is low.
The content of the invention
It is an object of the invention to provide a kind of host material is used as using defect as the centre of luminescence, using multi-component oxide
Novel green long after glow luminous material and preparation method thereof.The long after glow luminous material that the present invention synthesizes is using defect as in lighting
The heart, compared with conventionally employed rare earth ion or transition metal ions are as the long after glow luminous material of the centre of luminescence, preparation technology
Simply, cost is low and luminescent properties are excellent, after light-illuminating 15 minutes, can continue in the dark green light 14 hours with
On.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of multi-component oxide long after glow luminous material, its chemical expression are（2-a-b）ZnO·（1-c）SiO2·
0.4cP2O5·aMgO·dB2O3, wherein a=0.005 ~ 0.1, b=0.002 ~ 0.09, c=0.01 ~ 0.15, d=0.05 ~ 0.2.
The preparation method of the multi-component oxide long after glow luminous material, comprises the following steps：
1）MgO, ZnO, SiO are stoichiometrically weighed respectively2、(NH4)2HPO4And B2O3；
2）Load weighted each material mixing it is good after be placed in ball grinder and add absolute ethyl alcohol to 3/4ths of tank volume, lid
Tight lid was placed in ball mill with 800 turns per minute of rotating speed ball milling 3-6 hours, was placed in after taking-up in drying box at 120 DEG C
Air-dry 6 hours acquisition white powders；
3）White powder is placed in crucible, at 950-1200 DEG C in air calcine 1-5 hours, then in a vacuum in
Continue to calcine 2-6 hours at 950-1200 DEG C, obtain the luminescent material.
The beneficial effects of the present invention are：
The present invention, wherein using silicon, zinc oxide as material of main part, is suitably introduced into magnesium using multi-component oxide as host material
And boron oxide compound can effectively improve structural behaviour and the crystal property of material so as to be advantageous to the improvement of material emission performance, phosphorus
The incorporation of element also can effectively improve the luminescent properties of material.Prepared stability of material is good, cost is low and good luminous performance,
In the dark it is observed that bright-coloured green glow, range estimation persistence are more than 14 hours after light irradiates 15 minutes.
Brief description of the drawings
Fig. 1 is the gained green long afterglow luminescent material 1.96ZnO0.99SiO of embodiment 12·0.004P2O5·
0.01MgO·0.08B2O3X-ray diffraction pattern；
Fig. 2 is the gained green long afterglow luminescent material 1.96ZnO0.99SiO of embodiment 12·0.004P2O5·0.01MgO·
0.08B2O3Excitation and emission spectra figure；
Fig. 3 is the gained green long afterglow luminescent material 1.96ZnO0.99SiO of embodiment 12·0.004P2O5·0.01MgO·
0.08B2O3Thermoluminescence.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of multi-component oxide long after glow luminous material, its chemical expression are 1.96ZnO0.99SiO2·
0.004P2O5·0.01MgO·0.08B2O3, preparation method comprises the following steps：
1）MgO, ZnO, SiO are stoichiometrically weighed respectively2、(NH4)2HPO4And B2O3；
2）Load weighted each material mixing it is good after be placed in ball grinder and add absolute ethyl alcohol to 3/4ths of tank volume, lid
Tight lid is placed in ball mill with 800 turns per minute of rotating speed ball milling 5 hours, is placed in after taking-up in drying box in 120 DEG C of leewards
Do 6 hours acquisition white powders；
3）White powder is placed in crucible, calcined 3 hours in air at 1050 DEG C, then in a vacuum at 1050 DEG C
Continue calcining 4 hours, obtain the luminescent material.
XRD tests show that prepared product thing mutually belongs to XRD standard diagram PDF 37-1485, as shown in Figure 1.
There is the wide of multiple excitation peaks between 300-450nm for the material prepared by the present invention as can be seen from Figure 2
Excitation spectrum band, its emission peak main peak, which is located at 521 nm, falls into green light band scope.
It is almost straight line that the heat for the material calcined in atmosphere as can be seen from Figure 3, which releases peak, i.e. defect density is very low
And the material of calcination processing releases bands of a spectrum between 360-430 K in the presence of a very strong and wide heat in a vacuum, Gauss is used
Approximating method can be fitted to 2 peaks and be located at 370 K and 406 K respectively, illustrate that there is two kinds of defects.
By obtained luminescent material after light irradiates 15 minutes in the dark it is observed that bright-coloured green glow, when estimating twilight sunset
Between be more than 14 hours.
Embodiment 2
A kind of multi-component oxide long after glow luminous material, its chemical expression are 1.993ZnO0.92SiO2·
0.032P2O5·0.005MgO·0.05B2O3, wherein a=0.005 ~ 0.1, b=0.002 ~ 0.09, c=0.01 ~ 0.15, d=0.05 ~
0.2, preparation method comprises the following steps：
1）MgO, ZnO, SiO are stoichiometrically weighed respectively2、(NH4)2HPO4And B2O3；
2）Load weighted each material mixing it is good after be placed in ball grinder and add absolute ethyl alcohol to 3/4ths of tank volume, lid
Tight lid is placed in ball mill with 800 turns per minute of rotating speed ball milling 3 hours, is placed in after taking-up in drying box in 120 DEG C of leewards
Do 6 hours acquisition white powders；
3）White powder is placed in crucible, calcines 5 hours in air at 950 DEG C, then in a vacuum at 950 DEG C after
Continuous calcining 6 hours, obtains the luminescent material.
By obtained luminescent material after light irradiates 15 minutes in the dark it is observed that bright-coloured green glow, when estimating twilight sunset
Between be more than 14 hours.
Embodiment 3
A kind of multi-component oxide long after glow luminous material, its chemical expression are 1.81ZnO0.85SiO2·0.06P2O5·
0.1MgO·0.2B2O3, wherein a=0.005 ~ 0.1, b=0.002 ~ 0.09, c=0.01 ~ 0.15, d=0.05 ~ 0.2, preparation method bag
Include following steps：
1）MgO, ZnO, SiO are stoichiometrically weighed respectively2、(NH4)2HPO4And B2O3；
2）Load weighted each material mixing it is good after be placed in ball grinder and add absolute ethyl alcohol to 3/4ths of tank volume, lid
Tight lid is placed in ball mill with 800 turns per minute of rotating speed ball milling 6 hours, is placed in after taking-up in drying box in 120 DEG C of leewards
Do 6 hours acquisition white powders；
3）White powder is placed in crucible, calcined 1 hour in air at 1200 DEG C, then in a vacuum at 1200 DEG C
Continue calcining 2 hours, obtain the luminescent material.
By obtained luminescent material after light irradiates 15 minutes in the dark it is observed that bright-coloured green glow, when estimating twilight sunset
Between be more than 14 hours.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (2)
- A kind of 1. multi-component oxide long after glow luminous material, it is characterised in that：The chemical expression of the luminescent material is（2- a-b）ZnO·（1-c）SiO2·0.4cP2O5·aMgO·dB2O3, wherein a=0.005 ~ 0.1, b=0.002 ~ 0.09, c=0.01 ~ 0.15, d=0.05 ~ 0.2.
- A kind of 2. preparation method of multi-component oxide long after glow luminous material as claimed in claim 1, it is characterised in that：Bag Include following steps：1）MgO, ZnO, SiO are stoichiometrically weighed respectively2、(NH4)2HPO4And B2O3；2）Load weighted each material mixing it is good after be placed in ball grinder and add absolute ethyl alcohol to 3/4ths of tank volume, lid Tight lid was placed in ball mill with 800 turns per minute of rotating speed ball milling 3-6 hours, was placed in after taking-up in drying box at 120 DEG C Air-dry 6 hours acquisition white powders；3）White powder is placed in crucible, at 950-1200 DEG C in air calcine 1-5 hours, then in a vacuum in Continue to calcine 2-6 hours at 950-1200 DEG C, obtain the luminescent material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835262A (en) * | 2019-11-20 | 2020-02-25 | 闽南师范大学 | Blue-green hard luminous stone with zirconium-niobium ion common luminous center and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058726A (en) * | 2007-05-29 | 2007-10-24 | 东海布莱特科技开发有限公司 | Silicate long lag luminescent materials |
| CN105969350A (en) * | 2016-06-03 | 2016-09-28 | 闽南师范大学 | Blue-green long-afterglow luminescent material and preparation method thereof |
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- 2017-10-30 CN CN201711029894.7A patent/CN107722978B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058726A (en) * | 2007-05-29 | 2007-10-24 | 东海布莱特科技开发有限公司 | Silicate long lag luminescent materials |
| CN105969350A (en) * | 2016-06-03 | 2016-09-28 | 闽南师范大学 | Blue-green long-afterglow luminescent material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835262A (en) * | 2019-11-20 | 2020-02-25 | 闽南师范大学 | Blue-green hard luminous stone with zirconium-niobium ion common luminous center and preparation method thereof |
| CN110835262B (en) * | 2019-11-20 | 2022-04-05 | 闽南师范大学 | Blue-green hard luminous stone with zirconium-neodymium ion common luminous center and preparation method thereof |
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