CN106010533B - A kind of accumulating type emitting red light stone and preparation method thereof - Google Patents
A kind of accumulating type emitting red light stone and preparation method thereof Download PDFInfo
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- CN106010533B CN106010533B CN201610385540.5A CN201610385540A CN106010533B CN 106010533 B CN106010533 B CN 106010533B CN 201610385540 A CN201610385540 A CN 201610385540A CN 106010533 B CN106010533 B CN 106010533B
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- accumulating type
- red light
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7777—Phosphates
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Abstract
The invention discloses a kind of accumulating type emitting red light stone and preparation method thereof, and it is using red long afterglow luminous material as material of main part, by itself and Al2O3Or ZrO2By weight percentage 80 99:1 20 is well mixed rear compressing, then is prepared through high-temperature calcination；The chemical formula of the red long afterglow luminous material is (Zn1‑α‑β‑γ‑λMnαSmβAγBλ)3(PO4)2, wherein A is Dy3+Or Pr3+, B Na+Or K+, α, β, γ, λ represent the mole coefficient of each element.Proportioning science of the present invention, raw materials are environmentally friendly material, aboundresources, and price is relatively low, preparation technology is simple, gained luminous stone is after ultra violet lamp 15 minutes, in dark place it is observed that bright-coloured feux rouges, range estimation persistence are 8 hours, and it is free of radioactive substance, cost is low, and outward appearance is sparkling and crystal-clear thorough after sanding and polishing, can exceed natural legendary luminous pearl.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of accumulating type emitting red light stone and preparation method thereof.
Background technology
Legendary luminous pearl is also known as fluorescence stone or luminous stone, at night it can be seen that its self-luminescence, is naturally-produced in the Nature
A kind of jewel, it is very precious.Some legendary luminous pearls are due to containing radio isotope, it is not necessary to are carried out by any outside energy
Excite, the activator contained by itself lights with regard to energy oneself excitation.Because the very rare price of natural legendary luminous pearl is also very high,
Ordinary people can not possess at all, and the legendary luminous pearl of permanent shining contains harmful radio isotope.With long afterglow
Light-storing material makes luminous stone, copies natural legendary luminous pearl, can fulfill the dream that many people possess legendary luminous pearl, before having good business
Scape.
Patent of invention " a kind of energy-accumulating luminous stone and preparation method thereof "（CN101403475A）Disclose with long-persistence luminous
Material prepares the green that can turn blue, yellow green, purple and sapphire luminous stone with silica.But the patent fails to provide
The specific chemical composition of luminescent material used, it is that alumino-silicate may determine that it should be strontium aluminate or aluminic acid from its disclosed product
Calcium long after glow luminous material.And made the invention provides a kind of new phosphoric acid zinc-base red long afterglow luminous material, and with it
It is standby go out a kind of new accumulating type emitting red light stone.
The content of the invention
It is an object of the invention to provide a kind of accumulating type emitting red light stone and preparation method thereof, its raw material proportioning science is closed
Reason, manufacture craft is simple, low manufacture cost, and without radioactive substance, outward appearance, the quality of gained luminous stone can exceed natural night
Jewel.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of accumulating type emitting red light stone, it is with red long afterglow luminous material and Al2O3Or ZrO2For raw material preparation
Into；Red long afterglow luminous material and Al used2O3Or ZrO2The ratio between percetage by weight be 80-99:1-20.
The chemical formula of the red long afterglow luminous material is：(Zn1-α-β-γ-λMnαSmβAγBλ)3(PO4)2；Wherein, A is
Dy3+Or Pr3+, B Na+Or K+, α, β, γ, λ represent each element mole coefficient, its value be respectively α=0.001-0.05, β=
0.001-0.06、γ=0.001-0.06、λ=0.001-0.06。
The preparation method of the red long afterglow luminous material is：ZnO, MnCO are stoichiometrically weighed respectively3、
NH4H2PO4、Sm2O3、Pr2O3Or Dy2O3、Na2CO3Or K2CO3, while weigh prepared luminescent material molal weight 1-10% boron
Acid；It is placed in ball grinder after being mixed, by 200-600 r/min rotating speed ball milling 2-3h, is subsequently placed in filled with volumetric concentration
5%H2With 95%N2Reducing atmosphere stove in, in 900-1000 DEG C calcine 2-5h.
Wherein, Sm used2O3、Pr2O3、Dy2O3Purity be 99.99%, ZnO, MnCO used3、NH4H2PO4, boric acid,
Na2CO3、K2CO3It is that analysis is pure.
Al used2O3、ZrO2It is pure to analyze.
The preparation method of the accumulating type emitting red light stone be by proportioning weigh respectively red long afterglow luminous material with
Al2O3Or ZrO2, it is placed in after mixing in ball grinder, by 100-200 r/min rotating speed ball milling 0.5h, obtains well mixed mix
Compound, then mixture is molded using tabletting machine or using isostatic pressing under 2-20 atmospheric pressure, then put
In filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1050-1280 DEG C calcine 2-5h, produce.
The remarkable advantage of the present invention is：The invention provides a kind of accumulating type emitting red light stone, it is with Mn2+Ion is hair
The phosphoric acid zinc-base red illuminating material (Zn of light center1-α-β-γ-λMnαSmβAγBλ)3(PO4)2As material of main part, and by appropriate
Alundum (Al2O3) or zirconium oxide are introduced to improve the hardness of luminous stone.
Accumulating type emitting red light stone prepared by the present invention is observed that after UV illumination penetrates 15 minutes in darkroom
Its bright red sent；The initial strength of luminous stone is up to 2865 mcd/m2, range estimation persistence can reach 8 hours.
Brief description of the drawings
Fig. 1 is the XRD of accumulating type emitting red light stone and the comparison diagram of standard spectrogram prepared by the present invention.
Fig. 2 is the excitation-emission spectrogram of accumulating type emitting red light stone prepared by the present invention.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Sm used2O3、Pr2O3、Dy2O3Purity be 99.99%, ZnO, MnCO used3、NH4H2PO4、Na2CO3Or
K2CO3, boric acid, Al2O3、ZrO2It is that analysis is pure.
Embodiment 1
By chemical formula (Zn0.996Mn0.001Sm0.001Dy0.001Na0.001)3(PO4)2Stoichiometric proportion weigh respectively ZnO,
MnCO3、NH4H2PO4、Sm2O3、Dy2O3、Na2CO3, while weigh the boric acid of prepared luminescent material molal weight 1%；Mixed
It is placed in ball grinder after conjunction, by 200 r/min rotating speed ball milling 3h, is subsequently placed in filled with volumetric concentration 5%H2With 95%N2Reduction
In atmosphere furnace, 3h is calcined in 900 DEG C, obtains red long afterglow luminous material (Zn0.996Mn0.001Sm0.001Dy0.001Na0.001)3
(PO4)2。
The ratio between weight percent is 80:20, prepared red long afterglow luminous material and Al are weighed respectively2O3, mixing
After be placed in ball grinder, by 100 r/min rotating speed ball milling 0.5h, well mixed mixture is obtained, then using tablet press machine
Mixture compression molding under 2 atmospheric pressures, then it is placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in,
5h is calcined in 1050 DEG C, produces accumulating type emitting red light stone.Prepared luminous stone, can be certainly at dark place after ultraviolet light
Glow, 6 hours persistences.
Embodiment 2
By chemical formula (Zn0.975Mn0.01Sm0.005Dy0.005K0.005)3(PO4)2Stoichiometric proportion weigh respectively ZnO,
MnCO3、NH4H2PO4、Sm2O3、Dy2O3、K2CO3, while weigh the boric acid of prepared luminescent material molal weight 5%；It is mixed
After be placed in ball grinder, by 400 r/min rotating speed ball milling 2h, be subsequently placed in filled with volumetric concentration 5%H2With 95%N2Also Primordial Qi
In atmosphere stove, 5h is calcined in 950 DEG C, obtains red long afterglow luminous material (Zn0.975Mn0.01Sm0.005Dy0.005K0.005)3(PO4)2。
The ratio between weight percent is 85:15, prepared red long afterglow luminous material and ZrO are weighed respectively2, mixing
After be placed in ball grinder, by 150 r/min rotating speed ball milling 0.5h, well mixed mixture is obtained, then using tablet press machine
Mixture compression molding under 10 atmospheric pressures, then it is placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove
In, 3h is calcined in 1100 DEG C, produces accumulating type emitting red light stone.Prepared luminous stone is after ultraviolet light, at dark
It can glow certainly, 7 hours persistences.
Embodiment 3
By chemical formula (Zn0.95Mn0.02Sm0.01Pr0.01Na0.01)3(PO4)2Stoichiometric proportion weigh ZnO, MnCO respectively3、
NH4H2PO4、Sm2O3、Pr2O3、Na2CO3, while weigh the boric acid of prepared luminescent material molal weight 10%；It is mixed rearmounted
In ball grinder, by 600 r/min rotating speed ball milling 2h, it is subsequently placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove
In, 2h is calcined in 1000 DEG C, obtains red long afterglow luminous material (Zn0.95Mn0.02Sm0.01Pr0.01Na0.01)3(PO4)2。
The ratio between weight percent is 90:10, prepared red long afterglow luminous material and Al are weighed respectively2O3, mixing
After be placed in ball grinder, by 180 r/min rotating speed ball milling 0.5h, well mixed mixture is obtained, then using isostatic pressed
Mixture isostatic pressing under 5 atmospheric pressures, then it is placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove
In, 2h is calcined in 1200 DEG C, produces accumulating type emitting red light stone.Prepared luminous stone is after ultraviolet light, at dark
It can glow certainly, 8 hours persistences.
Embodiment 4
By chemical formula (Zn0.95Mn0.02Sm0.01Pr0.01Na0.01)3(PO4)2Stoichiometric proportion weigh ZnO, MnCO respectively3、
NH4H2PO4、Sm2O3、Pr2O3、K2CO3, while weigh the boric acid of prepared luminescent material molal weight 8%；It is placed in after being mixed
In ball grinder, by 500 r/min rotating speed ball milling 3h, it is subsequently placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove
In, 3h is calcined in 920 DEG C, obtains red long afterglow luminous material (Zn0.77Mn0.05Sm0.06Pr0.06K0.06)3(PO4)2。
The ratio between weight percent is 99:1, prepared red long afterglow luminous material and ZrO are weighed respectively2, mixing
After be placed in ball grinder, by 200 r/min rotating speed ball milling 0.5h, well mixed mixture is obtained, then using isostatic pressed
Mixture isostatic pressing under 20 atmospheric pressures, then it is placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove
In, 2h is calcined in 1280 DEG C, produces accumulating type emitting red light stone.Prepared luminous stone is after ultraviolet light, at dark
It can glow certainly, 5 hours persistences.
Fig. 1 is the XRD of accumulating type emitting red light stone and the comparison diagram of standard spectrogram prepared by embodiment 1.By can in figure
To find out, gained XRD spectra is with numbering the β-Zn for being 30-1489 in standard spectrogram3(PO4)2It is consistent.
Fig. 2 is the excitation-emission spectrogram of accumulating type emitting red light stone prepared by embodiment 1.As can be seen from Figure, its
There is individual emission peak at 616nm.
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 (5)
- A kind of 1. accumulating type emitting red light stone, it is characterised in that：With red long afterglow luminous material and Al2O3Or ZrO2For raw material It is prepared；Red long afterglow luminous material and Al used2O3Or ZrO2The ratio between percetage by weight be 80-99:1-20；The chemical formula of the red long afterglow luminous material is：(Zn1-α-β-γ-λMnαSmβAγBλ)3(PO4)2；Wherein, A Dy3+Or Pr3+, B Na+Or K+, the mole coefficient of α, β, γ, λ expression each element, its value is respectively α=0.001-0.05, β=0.001- 0.06、γ=0.001-0.06、λ=0.001-0.06；The preparation method of the accumulating type emitting red light stone is：Red long afterglow luminous material and Al are weighed respectively by proportioning2O3Or ZrO2, it is placed in after mixing in ball grinder, by 100-200 r/min rotating speed ball milling 0.5h, obtains well mixed mixture, so It is afterwards that mixture is compressing, it is placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1050-1280 DEG C calcining 2-5h, produce.
- 2. accumulating type emitting red light stone according to claim 1, it is characterised in that：Al used2O3、ZrO2It is pure to analyze.
- 3. accumulating type emitting red light stone according to claim 1, it is characterised in that：The red long afterglow luminous material Preparation method is：ZnO, MnCO are stoichiometrically weighed respectively3、NH4H2PO4、Sm2O3、Pr2O3Or Dy2O3、Na2CO3Or K2CO3, while weigh prepared luminescent material molal weight 1-10% boric acid；It is placed in after being mixed in ball grinder, by 200- 600 r/min rotating speed ball milling 2-3h, is subsequently placed in filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 900- 1000 DEG C of calcining 2-5h.
- 4. accumulating type emitting red light stone according to claim 3, it is characterised in that：Sm used2O3、Pr2O3、Dy2O3Purity It is 99.99%, ZnO, MnCO used3、NH4H2PO4, boric acid, Na2CO3、K2CO3It is that analysis is pure.
- 5. the preparation method of accumulating type emitting red light stone as claimed in claim 1, it is characterised in that：Weighed respectively by proportioning red Color long after glow luminous material and Al2O3Or ZrO2, it is placed in after mixing in ball grinder, by 100-200 r/min rotating speed ball milling 0.5h, well mixed mixture is obtained, it is then that mixture is compressing, it is placed in filled with volumetric concentration 5%H2With 95%N2Also In former atmosphere furnace, 2-5h is calcined in 1050-1280 DEG C, produces accumulating type emitting red light stone；It is described it is compressing be under 2-20 atmospheric pressure using tabletting machine be molded or using isostatic pressing.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403475A (en) * | 2008-11-13 | 2009-04-08 | 北京航空航天大学 | Energy accumulation luminous stone and its production method |
| CN101591533A (en) * | 2009-06-25 | 2009-12-02 | 郑子山 | A kind of red long afterglow luminous material and preparation method thereof |
| CN104804736A (en) * | 2015-04-30 | 2015-07-29 | 闽南师范大学 | Long-lasting phosphor material using defects as luminescence centers and preparation method of long-lasting phosphor material |
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2016
- 2016-06-03 CN CN201610385540.5A patent/CN106010533B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403475A (en) * | 2008-11-13 | 2009-04-08 | 北京航空航天大学 | Energy accumulation luminous stone and its production method |
| CN101591533A (en) * | 2009-06-25 | 2009-12-02 | 郑子山 | A kind of red long afterglow luminous material and preparation method thereof |
| CN104804736A (en) * | 2015-04-30 | 2015-07-29 | 闽南师范大学 | Long-lasting phosphor material using defects as luminescence centers and preparation method of long-lasting phosphor material |
Non-Patent Citations (1)
| Title |
|---|
| "A novel red long lasting phosphorescent (LLP) material β-Zn3(PO4)2:Mn2+, Sm3+";J. Wang et al.，;《Materials Research Bulletin》;20051231;第40卷(第4期);第590-598页 * |
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